Method for preparing silane derivatives from furan derivatives in presence of borane catalyst

Abstract

The present invention relates to a method for preparing various silane derivatives by subjecting various furan derivatives to hydrosilylation in the presence of a borane catalyst. The method for preparing silane derivatives according to the present invention is a very efficient method for converting, into high value-added silane derivatives, various furan derivatives derived from biomass.

Claims

1. A method of preparing a silane derivative represented by Chemical Formula 1, the method comprising preparing Chemical Formula 1 via a reaction between Chemical Formula 2 and Chemical Formula 3 in the presence of a borane catalyst: ##STR00109## wherein, in Chemical Formulae 1 to 3, R.sub.1 is C.sub.1-C.sub.10 alkyl or C.sub.6-C.sub.20 aryl with a radical number depending on n; R.sub.11 to R.sub.13 are each independently C.sub.1-C.sub.10 alkyl or C.sub.6-C.sub.12 aryl; n is an integer of 1 to 3 and, when n is equal to or greater than 2, R.sub.1 is aryl; and alkyl and aryl of R.sub.1 are further substituted with any one selected from halogen, C.sub.1-C.sub.10 alkyl, halo C.sub.1-C.sub.10 alkyl, thio C.sub.1-C.sub.10 alkyl, C.sub.1-C.sub.10 alkoxy, C.sub.6-C.sub.12 aryl, C.sub.6-C.sub.12 aryloxy, and OSi(R.sub.21)(R.sub.22)(R.sub.23) and R.sub.21 to R.sub.23 are each independently C.sub.1-C.sub.10 alkyl or C.sub.6-C.sub.12 aryl.

2. The method of claim 1, wherein Chemical Formula 1 is represented by Chemical Formula 1-1 and Chemical Formula 2 is represented by Chemical Formula 2-1: ##STR00110## wherein, in Chemical Formulae 1-1 and 2-1, R.sub.2 is C.sub.1-C.sub.10 alkyl or C.sub.6-C.sub.18 aryl; R.sub.11 to R.sub.13 are each independently C.sub.1-C.sub.10 alkyl or C.sub.6-C.sub.12 aryl; and alkyl and aryl of R.sub.2 are further substituted with any one selected from halogen, C.sub.1-C.sub.10 alkyl, halo C.sub.1-C.sub.10 alkyl, thio C.sub.1-C.sub.10 alkyl, C.sub.1-C.sub.10 alkoxy, C.sub.6-C.sub.12 aryl, C.sub.6-C.sub.12 aryloxy, and OSi(R.sub.21)(R.sub.22)(R.sub.23) and R.sub.21 to R.sub.23 are each independently C.sub.1-C.sub.10 alkyl or C.sub.6-C.sub.12 aryl.

3. The method of claim 1, wherein Chemical Formula 1 is represented by Chemical Formula 1-2 and Chemical Formula 2 is represented by Chemical Formula 2-2: ##STR00111## wherein, in Chemical Formulae 1-2 and 2-2, R.sup.11 to R.sup.13 are each independently C.sub.1-C.sub.10 alkyl or C.sub.6-C.sub.12 aryl; n is an integer of 1 to 3; R.sub.14 is halogen, C.sub.1-C.sub.10 alkyl, halo C.sub.1-C.sub.10 alkyl, thio C.sub.1-C.sub.10 alkyl, C.sub.1-C.sub.10 alkoxy, C.sub.6-C.sub.12 aryl, C.sub.6-C.sub.12 aryloxy, or OSi(R.sub.21)(R.sub.22)(R.sub.23); R.sub.21 to R.sub.23 are each independently C.sub.1-C.sub.10 alkyl or C.sub.6-C.sub.12 aryl; and s is an integer of 0 or 1 to 4 and n+s6.

4. The method of claim 1, wherein the borane catalyst is B(C.sub.6F.sub.5).sub.3, (C.sub.6F.sub.5CH.sub.2CH.sub.2)B(C.sub.6F.sub.5).sub.2, (CF.sub.3(CF.sub.2).sub.3(CH.sub.2).sub.2B(C.sub.6F.sub.5).sub.2, HB(C.sub.6F.sub.5).sub.2, B(C.sub.6H.sub.5).sub.3, or ClB(C.sub.6F.sub.5).sub.2.

5. The method of claim 1, wherein the borane catalyst is used in 0.01 to 0.03 mol based on 1 mol of the compound of Chemical Formula 2, Chemical Formula 5, Chemical Formula 7, Chemical Formula 9, or Chemical Formula 11.

6. The method of claim 1, wherein: Chemical Formula 3 is used in 2.0 to 2.5 moles based on 1 mol of the compound of Chemical Formula 2, Chemical Formula 5, Chemical Formula 7, or Chemical Formula 11; and Chemical Formula 3-1 is used in 2.0 to 2.5 moles based on 1 mol of the compound of Chemical Formula 9.

7. The method of claim 1, wherein the borane catalyst is B(C.sub.6F.sub.5).sub.3 and Chemical Formula 3 is PhMe.sub.2SiH.

Description

BEST MODE

(1) Reference will now be made in detail to the exemplary embodiments of the present invention, but the following exemplary embodiments are given for better understanding of the present invention and the scope of the present invention is not limited thereto.

(2) A furan derivative is synthesized and used using Preparation Examples 1 and 2 below.

Preparation Example 1 General Method of Preparing Furan Derivative

(3) ##STR00027##

(4) Aryl bromide or aryl iodide (1.0 equiv), boronic acid (1.1 to 1.5 equiv.), Pd(PPh.sub.3).sub.4 (5 to 10 mol %), and Cs.sub.2CO.sub.3 (1.1 to 1.4 equiv.) were put in a round bottom flask, toluene (content corresponding to 0.086 M of arylhalide) and methanol (content corresponding to 0.33 M of arylhalide) were added thereto, and the resultant was subjected to a reaction at 100 to 110 C. for 12 hours. When the reaction was completed, the reaction mixture was cooled to 23 C., was quenched with a saturated NH.sub.4Cl solution, and was subjected to extraction with ethyl acetate (20 mL3) and, then, an organic layer was washed with salt water (20 mL1). The collected organic layers were dried with MgSO.sub.4, were subjected to vacuum evaporation, and were isolated and purified via silica gel column chromatography to obtain a target compound.

(5) ##STR00028##
2-[4-(Trifluoromethyl)phenyl]furan 84%).

(6) Prepared from 1-bromo-4-(trifluoromethyl)benzene; colorless solid; m.p. 90-92 C.; .sup.1H NMR (600 MHz, CDCl.sub.3): 7.90-7.73 (m, 2H), 7.73-7.61 (m, 2H), 7.53 (s, 1H), 6.80 (s, 1H), 6.53 (s, 1H); .sup.13C NMR (100 MHz, CDCl.sub.3): 152.7, 143.2, 134.1, 129.2 (q, J=32.3 Hz), 128.9, 128.6, 125.9, 124.3 (q, J=272 Hz), 122.9, 112.1, 107.1; .sup.19F NMR (3751 MHz, CDCl.sub.3): 62.5; HRMS (EI): Calculated for C11H7F3O [M]+: 212.0449, Found: 212.0447.

(7) ##STR00029##
2-(4-Fluorophenyl)furan (84%).

(8) Prepared from 1-bromo-4-fluorobenzene; colorless solid; m.p. 32-34 C.; .sup.1H NMR (600 MHz, CDCl.sub.3): 7.73-7.58 (m, 2H), 7.54-77.40 (m, 1H), 7.09 (t, J=8.7 Hz, 2H), 6.59 (d, J=3.4 Hz, 1H), 6.48 (dd, J=3.3, 1.8 Hz, 1H); .sup.13C NMR (150 MHz, CDCl.sub.3): 162.3 (d, J=246.8 Hz), 153.3, 142.1, 127.4 (d, 3.2 Hz), 125.7 (d, J=8.0 Hz), 115.8 (d, J=21.9 Hz), 111.8, 104.8; .sup.19F NMR (565 MHz, CDCl.sub.3): 114.4; HRMS (EI): Calculated for C10H7FO [M]+: 162.0481, Found: 162.0483.

(9) ##STR00030##
2-(4-Chlorophenyl)furan (90%).

(10) Prepared from 1-bromo-4-chlorobenzene; colorless solid; m.p. 64-66 C.; .sup.1H NMR (600 MHz, CDCl.sub.3): 7.65-7.58 (m, 2H), 7.47 (d, J=1.9 Hz, 1H), 7.41-7.27 (m, 2H), 6.64 (d, J==3.4 Hz, 1H), 6.48 (dd, J=3.5, 1.8 Hz, 1H); .sup.13C NMR (150 MHz, CDCl.sub.3): 153.1, 142.5, 133.1, 129.5, 129.0, 125.2, 111.9, 105.6; HRMS (EI): Calculated for C10H7ClO [M]+: 178.0185, Found: 178.0186.

(11) ##STR00031##
2-(4-Bromophenyl)furan (52%).

(12) Prepared from 1,4-dibromobenzene; colorless solid; m.p. 75-77 C.; .sup.1H NMR (600 MHz, CDCl.sub.3): 7.54 (d, J=8.5 Hz, 2H), 7.50 (d, J=8.5 Hz, 2H), 7.47 (s, 1H), 6.66 (s, 1H), 6.47 (s, 1H); .sup.13C NMR (150 MHz, CDCl.sub.3): 153.1, 142.5, 131.9, 129.9, 125.4, 121.2, 111.9, 105.7; HRMS (EI): Calculated for C10H7BrO [M]+: 221.9680, Found: 221.9678.

(13) ##STR00032##
2-(1,1-Biphenyl-4-yl)furan (85%).

(14) Prepared from 4-bromo-1,1-biphenyl; colorless solid; m.p. 156-158 C.; .sup.1H NMR (600 MHz, CDCl.sub.3): 7.86-7.79 (m, 2H), 7.73-7.70 (m, 2H), 7.71-7.68 (m, 2H), 7.57 (dd, J=1.8, 0.8 Hz, 1H), 7.55-7.49 (m, 2H), 7.47-7.39 (m, 1H), 6.76 (dd, J=3.3, 0.8 Hz, 1H), 6.57 (dd, J=3.4, 1.8 Hz, 1H); .sup.13C NMR (150 MHz, CDCl.sub.3): 153.8, 142.2, 140.6, 140.0, 129.9, 128.9, 127.42, 127.41, 126.9, 124.3, 111.8, 105.2; HRMS (EI): Calculated for C16H12O [M]+: 220.0888, Found: 220.0890.

(15) ##STR00033##
2-Phenylfuran (92%).

(16) Prepared from 1-bromobenzene; colorless liquid; .sup.1H NMR (600 MHz, CDCl.sub.3): 7.77-7.67 (m, 2H), 7.51 (d, J=1.8 Hz, 1H), 7.42 (t, J=7.8 Hz, 2H), 7.30 (t, J=7.2, Hz, 1H), 6.69 (d, J=3.3 Hz, 1H), 6.51 (dd, J=3.4, 1.8 Hz, 1H); .sup.13C NMR (150 MHz, CDCl.sub.3): 154.1, 142.2, 131.0, 128.8, 127.5, 123.9, 111.8, 105.1

(17) ##STR00034##
2-(m-Tolyl)furan (86%).

(18) Prepared from 1-bromo-3-methylbenzene; colorless liquid; .sup.1H NMR (600 MHz, CDCl.sub.3): 7.57-7.45 (m, 3H), 7.29 (s, 1H), 7.09 (d, J=7.9 Hz, 1H), 6.65 (d, J=3.0 Hz, 1H), 6.48 (d, J=1.7 Hz, 1H), 2.40 (s, 3H); .sup.13C NMR (150 MHz, CDCl.sub.3): 154.1, 141.9, 138.2, 130.8, 128.5, 128.1, 124.4, 120.9, 111.5, 104.8, 21.5

(19) ##STR00035##
2-(4-Phenoxyphenyl)furan (91%).

(20) Prepared from 1-bromo-4-phenoxybenzene; colorless solid; m.p. 63-65 C.; .sup.1H NMR (600 MHz, CDCl.sub.3): 7.65 (d, J=8.4 Hz, 2H), 7.46 (s, 1H), 7.36 (t, J=7.7 Hz, 2H), 7.13 (t, J=7.4 Hz, 1H), 7.04 (dd, J=8.2, 5.8 Hz, 4H), 6.59 (s, 1H), 6.48 (s, 1H); .sup.13C NMR (150 MHz, CDCl.sub.3): 157.2, 156.8, 153.8, 141.9, 129.9, 126.5, 125.5, 123.5, 119.2, 119.1, 111.8, 104.4; HRMS (EI): Calculated for C16H12O2 [M]+: 236.0837, Found: 236.0835.

(21) ##STR00036##
2-[4-(Methylthio)phenyl]furan 83%).

(22) Prepared from (4-bromophenyl)(methyl)sulfane; brown color solid; m.p. 79-81 C.; .sup.1H NMR (600 MHz, CDCl.sub.3): 7.63 (d, J=8.2, Hz, 2H), 7.48-7.40 (m, 1H), 7.26 (d, J=8.4 Hz, 2H), 6.60 (t, J=3.3 Hz, 1H), 6.48-6.42 (m, 1H), 2.49 (s, 3H); .sup.13C NMR (150 MHz, CDCl.sub.3): 153.6, 141.8, 137.5, 127.9, 126.8, 124.2, 111.6, 104.6, 15.8; HRMS (EI): Calculated for C11H10OS [M]+: 190.0452, Found: 190.0452.

Preparation Example 2 General Method of Preparing Furanyl Alcohol Derivative Protected with Silyl Group

(23) ##STR00037##

(24) CH.sub.2Cl.sub.2 (5 mL) was put in a dried flask, alcohol (1.0 equiv.) synthesized and prepared at 0 C. using the same way as in Preparation Example 1 was added thereto, imidazole (1.3 equiv.) was slowly added thereto at the same temperature and, then, was stirred for 10 minutes, silyl chloride (1.2 equiv.) melted in CH.sub.2Cl.sub.2 (10 mL) was added thereto, and the resultant was subjected to a reaction at 23 C. for 12 hours. The reaction mixture was quenched with a saturated NH.sub.4Cl solution, and was subjected to extraction with ethyl acetate (20 mL3) and, then, an organic layer was washed with salt water (10 mL1). The collected organic layers were dried anhydrous Na.sub.2SO.sub.4, were subjected to vacuum evaporation, and were isolated and purified via column chromatography to obtain a target compound.

(25) ##STR00038##
[4-(Furan-2-yl)phenoxy]triisopropylsilane (76%)

(26) Prepared from 4-iodophenol; colorless liquid; .sup.1H NMR (600 MHz, CDCl.sub.3): 7.61-7.52 (m, 2H), 7.43 (d, J=2.0 Hz, 1H), 7.01-6.88 (m, 2H), 6.52 (d, J=3.4 Hz, 1H.), 6.45 (dd, J=3.4, 1.8 Hz, 1H), 1.34-1.25 (m, 3H), 1.14 (d, J=7.4 Hz, 18H); .sup.13C NMR (150 MHz, CDCl.sub.3): 155.8, 154.3, 141.5, 125.3, 124.5, 120.3, 111.7, 103.5, 18.1, 12.9; 29Si NMR (120 MHz, CDCl3): 15.7; HRMS (EI): Calculated for C19H28O2Si [M]+: 316.1859, Found: 316.1858.

(27) ##STR00039##
2-(3,5-Dibromophenyl)furan (56%)

(28) Prepared from 1,3,5-tribromobenzene; colorless solid; m.p. 44-46 C.; .sup.1H NMR (600 MHz, CDCl.sub.3): 7.72 (t, J=1.6 Hz, 2H), 7.52 (d, J=1.8 Hz, 1H), 7.47 (s, 1H), 6.68 (dd, J=3.2, 1.6 Hz, 1H), 6.52-6.42 (m, 1H); .sup.13C NMR (150 MHz, CDCl.sub.3): 150.8, 143.2, 133.9, 132.3, 125.3, 123.24, 111.9, 107.1; HRMS (EI): Calculated for C10H6Br2O [M]+: 299.8785, Found: 299.8786.

(29) ##STR00040##
2-(2,4,6-Triisopropylphenyl)furan (28%)

(30) Prepared from 2-bromo-1,3,5-triisopropylbenzene; colorless solid; m.p. 103-105 C.; .sup.1H NMR (600 MHz, CDCl.sub.3): 7.53 (d, J=1.9 Hz, 1H), 7.10 (s, 2H), 6.76-6.45 (m, 1H), 6.29 (d, J=3.2 Hz, 1H), 3.06-2.88 (m, 1H), 2.80-2.63 (m, 2H), 1.33 (d, J=6.9 Hz, 6H), 1.19 (d, J=6.9 Hz, 12H); .sup.13C NMR (150 MHz, CDCl.sub.3): 152.3, 150.2, 149.7, 141.6, 126.8, 120.8, 110.3, 109.4, 34.6, 30.9, 24.4, 24.2; HRMS (EI): Calculated for C19H26O [M]+: 270.1984, Found: 270.1982.

(31) ##STR00041##
2-(Phenanthren-9-yl)furan (79%)

(32) Prepared from 9-bromophenanthrene; colorless solid; m.p. 86-88 C.; .sup.1H NMR (600 MHz, CDCl.sub.3): 8.87-8.78 (m, 1H), 8.76-8.70 (m, 1H), 8.66-857 (m, 1H), 8.15 (d, J=3.4 Hz, 1H), 8.00 (dd, J=7.9, 3.4 Hz, 1H), 7.82-7.65 (m, 5H), 6.91 (s, 1H), 6.73 (s, 1H); .sup.13C NMR (150 MHz, CDCl.sub.3): 153.5, 142.5, 131.4, 130.9, 130.3, 129.7, 129.0, 127.5, 127.4, 127.1, 126.9, 126.9, 126.7, 126.4, 123.1, 122.6, 111.5, 109.7; HRMS (EI): Calculated for C8H12O [M]+: 244.0888, Found: 244.0887.

(33) ##STR00042##
1,4-Di(furan-2-yl)benzene (13%).

(34) Prepared from 1,4-dibromobenzene; yellow color solid; m.p. 135-140 C.; .sup.1H NMR (600 MHz, CDCl.sub.3): 7.83-7.61 (m, 4H), 7.47 (d, J=1.8 Hz, 2H), 6.66 (d, J=3.3 Hz, 2H), 6.48 (dd, J=3.4, 1.8 Hz, 2H); .sup.13C NMR (150 MHz, CDCl.sub.3): 153.9, 142.3, 129.9, 124.2, 111.9, 105.3; HRMS (EI): Calculated for C14H10O2 [M]+: 210.0681, Found: 210.0677.

(35) ##STR00043##
2,2-(5-Bromo-1,3-phenylene)difuran (8%)

(36) Prepared from 1,3,5-tribromobenzene; colorless solid; m.p. 77-79 C.; .sup.1H NMR (600 MHz, CDCl.sub.3): 7.86 (d, J=2.0 Hz, 1H), 7.67 (t, J=1.7 Hz, 2H), 7.49 (d, J=2.6 Hz, 2H), 6.71 (t, J=2.7 Hz, 2H), 6.49 (dt, J=3.4, 1.8 Hz, 2H); 13C NMR (150 MHz, CDCl3): 152.1, 142.7, 132.9, 125.2, 123.1, 117.5, 111.8, 106.4.

(37) ##STR00044##
1,3,5-Tri(furan-2-yl)benzene (81%)

(38) Prepared from 1,3,5-tribromo-benzene; colorless solid; m.p. 138-140 C.; .sup.1H NMR (600 MHz, CDCl.sub.3): 7.90 (s, 3H), 7.53 (d, J=2.3 Hz, 3H), 6.78 (d, J=3.2 Hz, 3H), 6.52 (dd, J=3.5, 1.8 Hz, 3H); .sup.13C NMR (150 MHz, CDCl.sub.3): 153.4, 142.3, 131.6, 118.0, 111.7, 105.7; HRMS (EI): Calculated for C18H12O3 [M]+: 276.0786, Found: 276.0787.

(39) ##STR00045##
3-[4-(tert-Butyl)phenyl]furan (68%)

(40) Prepared from 3-bromofuran; colorless solid; m.p. 59-61 C.; .sup.1H NMR (600 MHz, CDCl.sub.3): 7.73 (s, 1H), 7.49 (s, 1H), 7.44 (q, J=7.9 Hz, 4H), 6.72 (s, 1H), 1.37 (s, 9H); .sup.13C NMR (150 MHz, CDCl.sub.3): 150.1, 143.6, 138.4, 129.7, 126.4, 125.8, 125.8, 109.1, 34.7, 31.5; HRMS (EI): Calculated for C14H16O [M]+: 200.1201, Found: 200.1199.

(41) ##STR00046##
[4-(Benzofuran-2-yl)phenoxy]triisopropylsilane (83%).

(42) Prepared from 4-iodophenol; colorless solid; m.p. 46-48 C.; .sup.1H NMR (600 MHz, CDCl.sub.3): 7.74 (d, J=8.7 Hz, 2H), 7.55 (d, J=6.9 Hz, 1H), 7.50 (d, J=8.1 Hz, 1H), 7.33-7.17 (m, 2H), 6.96 (d, J=8.7 Hz, 2H), 6.88 (s, 1H), 1.41-1.20 (m, 3H), 1.14 (d, 9H), 1.14 (d, 9H); .sup.13C NMR (150 MHz, CDCl.sub.3): 156.9, 156.3, 154.9, 129.7, 126.5, 123.8, 123.8, 122.9, 120.7, 120.4, 111.1, 99.8, 18.1, 12.9; .sup.29Si NMR (120 MHz, CDCl.sub.3): 16.1; HRMS (EI): Calculated for C23H30O2Si [M]+: 366.2015, Found: 366.2018.

(43) ##STR00047##
2-Phenylbenzofuran (89%)

(44) Prepared from 1-bromobenzene; colorless liquid; .sup.1H NMR (600 MHz, CDCl.sub.3): 7.97 (d, J=7.2 Hz, 2H), 7.68 (d, J=8.1 Hz, 1H), 7.63 (d, J=8.7 Hz, 1H), 7.55 (t, J=7.7 Hz, 2H), 7.45 (t, J=6.3 Hz, 1H), 7.38 (t, J=7.7 Hz, 1H), 7.36-7.30 (m, 1H), 7.12 (s, 1H); .sup.13C NMR (150 MHz, CDCl.sub.3): 156.1, 155.1, 130.7, 129.4, 128.9, 128.7, 125.1, 124.4, 123.1, 121.0, 111.3, 101.5; HRMS (EI): Calculated for C14H10O [M]+: 194.0732, Found: 194.0730.

(45) ##STR00048##
2-[(1,1-Biphenyl)-4-ylmethyl]furan (92%)

(46) Prepared from 4-(bromomethyl)-1,1-biphenyl; colorless solid; m.p. 81-83 C.; .sup.1H NMR (600 MHz, CDCl.sub.3) 7.60 (d, J=7.8 Hz, 2H), 7.56 (d, J=8.0 Hz, 2H), 7.45 (t, J=7.6 Hz, 2H), 7.37 (s, 1H), 7.36-7.31 (m, 3H), 6.34 (s, 1H), 6.08 (s, 1H), 4.04 (s, 2H); .sup.13C NMR (150 MHz, CDCl.sub.3) 154.6, 141.7, 141.1, 139.6, 137.4, 129.2, 128.9, 127.4, 127.3, 127.2, 110.4, 106.5, 34.3; HRMS (EST): Calculated for C17H14ONa [M+Na]+: 257.0942, Found: 257.0911.

(47) A silane derivative was synthesized according to the following exemplary embodiments using the furan derivatives prepared in Preparation Examples 1 and 2 above.

I. Preparation of Silyloxyalkenyl Silane Derivative

Inventive Example 1 General Preparation of (Z)--silyloxyalkenylsilane (Derivative Silyloxyalkenylsilanes)

(48) ##STR00049##

(49) CH.sub.2Cl.sub.2 (0.4-0.8 mL) and B(C.sub.6F.sub.5).sub.3 (0.01 to 0.02 mmol, 2.0 mol %) were put in a dried flask, a silane compound (PhMe.sub.2SiH, 1.025 to 2.050 mmol) was added thereto and was well stirred and, then, a furan derivative (0.50 to 1.0 mmol) was again added thereto and, then, was stirred at 23 C. for 1 to 5 hours. The reaction mixture was quenched with Et3N (5.0 to 10.0 mol %), was subjected to vacuum evaporation, and was isolated and purified (to nucleic acid or hexane and ethyl acetate) via silica gel column chromatography to obtain a target product (Z/E>99/1).

(50) The following compound was prepared using the same method as the above.

(51) ##STR00050##

(52) (Z)-[1-(Dimethylphenylsilyloxy)pent-3-en-1-yl]dimethylphenylsilane (95%). The compound was prepared by stirring 2-methylfuran (3.284 g, 40 mmol) and dimethylphenylsilane (11.18 g, 82 mmol) at 23 C. for 12 hours in the presence of B(C.sub.6F.sub.5).sub.3 (409.6 mg, 2.0 mol %) melted in CH.sub.2C.sub.12 (8 mL) under argon gas, and had a conversion yield of >95% from analysis via .sup.1H NMR. Yield of 91% (12.88 g);

(53) colorless liquid; .sup.1H NMR (600 MHz, CDCl3): 7.66-7.57 (m, 4H), 7.50-67.38 (m, 6H), 5.52-5.40 (m, 2H), 3.75 (t, J=6.9 Hz, 1H), 2.44-2.30 (m, 2H), 1.56 (dd, J=6.6, 1.6 Hz, 3H), 0.39 (s, 6H), 0.36 (s, 3H), 0.35 (s, 3H); .sup.13C NMR (100 MHz, CDCl.sub.3): 138.8, 137.8, 134.4, 133.8, 129.4, 129.1, 128.4, 127.7 (2C), 125.1, 66.9, 32.0, 13.0, 0.8, 0.9, 4.5, 4.7; .sup.29Si NMR (120 MHz, CDCl.sub.3): 6.0, 4.2; HRMS (EI): Calculated for C21H30OSi2 [M]+: 354.1835, Found: 354.1831.

(54) ##STR00051##

(55) (Z)-1-(Dimethylphenylsilyl)hex-3-en-1-ol (86%). (i) Preparation was performed via a reaction between dimethylphenylsilane (279 mg, 2.1 mmol) and 2-ethylfuran (96 mg, 1.0 mmol) at 23 C. for 1.5 hours in the presence of B(C.sub.6F.sub.5).sub.3 (10.2 mg, 2.0 mol %) melted in CH.sub.2Cl.sub.2 (0.8 ml) under argon gas. After the reaction was completed, K.sub.2CO.sub.3 (276 mg, 2.00 mmol) obtained by melting the reaction mixture in MeOH (2 mL) was added and was subjected to a reaction at 23 C. for 4 hours (201.5 mg, 86% for two steps).

(56) colorless liquid; .sup.1H NMR (600 MHz, CDCl.sub.3): 7.70-7.57 (m, 2H), 7.48-7.30 (m, 3H), 5.97-5.57 (m, 1H), 5.45-5.10 (m, 1H), 3.50 (d, J=10.6 Hz, 1H), 2.40 (q, J=12 Hz, 1H), 2.28-2.17 (m, 1H), 2.07 (d, J=6.7 Hz, 2H), 1.56 (brs, 1H), 0.99 (t, J=6.7 Hz, 3H), 0.42 (s, 3H), 0.41 (s, 3H); .sup.13C NMR (150 MHz, CDCl.sub.3): 136.9, 135.3, 134.2, 129.3, 127.9, 125.9, 64.5, 31.4, 20.7, 14.4, 5.3, 5.5; .sup.29Si NMR (120 MHz, CDCl.sub.3): 3.8; HRMS (EI): Calculated for C14H22OSi [M]+: 234.1440, Found 234.1440.

(57) ##STR00052##

(58) (Z)-[1-(Dimethylphenylsilyloxy)hept-3-en-1-yl]dimethylphenylsilane (92%). The compound was prepared from 2-propylfuran.

(59) colorless liquid; .sup.1H NMR (600 MHz, CDCl.sub.3): 7.60-7.51 (m, 4H), 7.32-7.42 (m, 6H), 5.56-5.17 (m, 2H), 3.66 (t, J=6.9 Hz, 1H), 2.67-2.23 (m, 2H), 1.87 (q, J=6.6 Hz, 2H), 1.37-1.26 (m, 2H), 0.87 (t, J=7.4 Hz, 3H), 0.32 (s, 6H), 0.29 (s, 3H), 0.28 (s, 3H); .sup.13C NMR (150 MHz, CDCl.sub.3): 138.8, 137.8, 134.4, 133.8, 131.0, 129.4, 129.1, 127.7 (2C), 127.5, 67.1, 32.4, 29.5, 22.9, 13.9, 0.7, 0.9, 4.5, 4.7; .sup.29Si NMR (120 MHz, CDCl.sub.3): 5.9, 4.3; HRMS (EI): Calculated for C23H34OSi2 [M]+: 383.2148, Found: 382.2144.

(60) ##STR00053##

(61) (Z)-1-[(Dimethylphenylsilyloxy)-non-3-en-1-yl]dimethylphenylsilane (reaction time: 1 h, 86%). The compound was prepared from 2-pentylfuran.

(62) colorless liquid; .sup.1H NMR (600 MHz, CDCl.sub.3): 7.57-7.48 (m, 4H), 7.42-7.31 (m, 6H), 5.41-5.12 (m, 2H), 3.65 (t, J=6.9 Hz, 1H), 2.34-2.23 (m, 2H), 1.94-1.82 (m, 2H), 1.33-1.26 (m, 4H), 1.26-1.17 (m, 2H), 0.90 (t, J=7.1 Hz, 3H), 0.31 (s, 6H), 0.28 (s, 3H), 0.27 (s, 3H); .sup.13C NMR (150 MHz, CDCl.sub.3): 138.8, 137.8, 134.4, 133.79, 131.3, 129.4, 129.1, 127.7 (2C), 127.3, 67.1, 32.4, 31.70, 29.4, 27.5, 22.7, 14.2, 0.7, 0.9, 4.5, 4.7; .sup.29Si NMR (120 MHz, CDCl.sub.3): 5.9, 4.3; HRMS (ESI): Calculated for C25H38ONaSi2 [M+Na]+: 433.2359, Found: 433.2368.

(63) ##STR00054##

(64) (Z)-1-[(Dimethylphenylsilyloxy)-4-(4-trifluoromethylphenyl)but-3-en-1-yl]dimethylphenylsilane (reaction time: 4 h, 90%). The compound was prepared from 2-[4-(trifluoromethyl)phenyl]furan.

(65) colorless liquid; .sup.1H NMR (600 MHz, CDCl.sub.3): 7.62-7.57 (m, 1H), 7.54 (d, J=6.8 Hz, 2H), 7.52-7.46 (m, 3H), 7.41-7.34 (m, 5H), 7.33-7.27 (m, 3H), 6.39 (d, J=11.7 Hz, 1H), 5.75 (dt, J=11.7, 7.4 Hz, 1H), 3.77 (dd, J=8.0, 5.2 Hz, 1H), 2.65-2.55 (m, 1H), 2.50-2.41 (m, 1H), 0.38 (s, 3H), 0.31 (s, 6H), 0.30 (s, 3H); .sup.13C NMR (150 MHz, CDCl.sub.3): 141.1, 138.4, 137.2, 134.3, 133.8, 133.1, 129.6, 129.3, 129.0, 128.9, 127.8 (2C), 126.2, 125.1 (q, J=4.5 Hz), 124.5 (q, J=273 Hz), 66.8, 33.2, 0.8, 0.9, 4.7, 4.9; .sup.29Si NMR (120 MHz, CDCl.sub.3): 6.6, 4.0; .sup.19F NMR (565 MHz, CDCl3) 1114.4; HRMS (ESI): Calculated for C27H31F3NaOSi2 [M+Na]+: 507.1763, Found: 507.1771.

(66) ##STR00055##

(67) (Z)-1-[(Dimethylphenylsilyloxy)-4-(4-fluorophenyl)but-3-en-1-yl]dimethylphenylsilane (reaction time: 1.5 h, 85%). The compound was prepared from 2-(4-fluorophenyl)furan.

(68) colorless liquid; .sup.1H NMR (600 MHz, CDCl.sub.3): 7.53 (d, J=6.7 Hz, 2H), 7.47 (d, J=7.2 Hz, 2H), 7.41-7.30 (m, 6H), 7.18-7.12 (m, 2H), 6.99-6.90 (m, 2H), 6.33 (d, J=11.6 Hz, 1H), 5.62 (dt, J=11.3, 7.3 Hz, 1H), 3.74 (dd, J=7.9, 5.5 Hz, 1H), 2.58 (dt, J=15.6, 8.0 Hz, 1H), 2.45 (dt, J=15.1, 6.0 Hz, 1H), 0.30 (s, 3H), 0.29 (s, 6H), 0.28 (s, 3H); .sup.13C NMR (150 MHz, CDCl.sub.3): 161.6 (d, J=246.0 Hz) 138.5, 137.4, 134.4, 133.8, 133.6 (d, J=3.0 Hz), 133.1, 130.7, 130.4 (d, J=8.0 Hz), 129.5, 129.2, 128.9, 127.8, 115.0 (d, J=21.0 Hz), 66.9, 33.1, 0.8, 0.9, 4.7, 4.9; .sup.29Si NMR (120 MHz, CDCl3): 6.5, 4.1; .sup.19F NMR (375 MHz, CD.sub.2Cl.sub.2): 115.9; HRMS (EI): Calculated for C26H31FOSi2 [M]+: 434.1897, Found: 434.1901.

(69) ##STR00056##

(70) (Z)-1-[(Dimethylphenylsilyloxy)-4-(4-chlorophenyl)but-3-en-1-yl]dimethylphenylsilane (reaction time: 2 h, 86%). The compound was prepared from 2-(4-chlorophenyl)furan.

(71) colorless liquid; .sup.1H NMR (600 MHz, CDCl.sub.3): 7.56-7.52 (m, 2H), 7.47 (d, J=7.2 Hz, 2H), 7.42-7.30 (m, 6H), 7.23 (d, J=8.1 Hz, 2H), 7.12 (d, J=8.2 Hz, 2H), 6.32 (d, J=11.6 Hz, 1H), 5.65 (dt, J=11.7, 7.5 Hz, 1H), 3.75 (dd, J=8.0, 5.5 Hz, 1H), 2.69-2.53 (m, 1H), 2.48-2.29 (m, 1H), 0.30 (s, 9H), 0.29 (s, 3H); .sup.13C NMR (150 MHz, CDCl.sub.3): 138.5, 137.3, 136.0, 134.4, 133.8, 132.3, 131.5, 130.1, 129.5, 129.3, 128.9, 128.3, 127.80, 127.78, 66.8, 33.2, 0.8, 0.9, 4.7, 4.9; .sup.29Si NMR (120 MHz, CDCl.sub.3): 6.5, 4.1; HRMS (EI): Calculated for C26H31ClOSi2 [M]+: 450.1602, Found: 450.1600.

(72) ##STR00057##

(73) (Z)-1-[(Dimethylphenylsilyloxy)-4-(4-bromophenyl)but-3-en-1-yl]dimethylphenylsilane (reaction time: 2 h, 91%). The compound was prepared from 2-(4-bromophenyl)furan.

(74) Colorless liquid; .sup.1H NMR (600 MHz, CDCl.sub.3): 7.53 (d, J=9.2 Hz, 2H), 7.47 (d, J=7.9 Hz, 2H), 7.42-7.30 (m, 8H), 7.06 (d, J=8.3 Hz, 2H), 6.30 (d, J=11.7 Hz, 1H), 5.89-5.56 (m, 1H), 3.79-3.70 (m, 1H), 2.58 (dd, J=15.7, 7.5 Hz, 1H), 2.51-2.36 (m, 1H), 0.30 (s, 6H), 0.30 (s, 3H), 0.29 (s, 3H); .sup.13C NMR (150 MHz, CDCl.sub.3): 138.5, 137.3, 136.4, 134.3, 133.8, 131.6, 131.2, 130.4, 129.5, 129.3, 128.9, 127.80, 127.78, 120.4, 66.8, 33.1, 0.8, 0.9, 4.7, 4.9; .sup.29Si NMR (120 MHz, CDCl.sub.3): 6.5, 4.1; HRMS (EI): Calculated for C26H31BrOSi2 [M]+: 494.1097, Found: 494.1092.

(75) ##STR00058##

(76) (Z)-{4-[(1,1-Biphenyl)-4-yl]-1-(dimethylphenylsilyloxy)but-3-en-1-yl dimethylphenylsilane (reaction time: 3 h, 92%). The compound was prepared from 2-(1,1-biphenyl-4-yl)furan.

(77) colorless liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): 7.86-7.79 (m, 2H), 7.79-7.74 (m, 2H), 7.73-7.67 (m, 4H), 7.64 (t, J=7.6 Hz, 2H), 7.58-7.46 (m, 9H), 6.63 (d, J=11.7 Hz, 1H), 5.95-5.81 (m, 1H), 4.00 (dd, J=7.8, 5.6 Hz, 1H), 2.98-2.84 (m, 1H), 2.84-2.70 (m, 1H), 0.53 (s, 3H), 0.52 (s, 6H), 0.51 (s, 3H); .sup.13C NMR (100 MHz, CDCl.sub.3): 141.1, 139.36, 138.6, 137.4, 136.7, 134.5, 133.9, 131.1, 129.7, 129.6, 129.4, 129.3, 128.9, 127.9 (2C), 127.4, 127.1, 126.9, 67.1, 33.4, 0.6, 0.7, 4.6, 4.7; .sup.29Si NMR (80 MHz, CDCl.sub.3): 6.6, 3.9; HRMS (ESI): Calculated for C32H36NaOSi2 [M+Na]+: 515.2202, Found: 515.2200.

(78) ##STR00059##

(79) (Z)-1-[(Dimethylphenylsilyloxy)-4-phenylbut-3-en-1-yl]dimethylphenylsilane (reaction time: 2 h, 91%). The compound was prepared from 2-phenylfuran.

(80) colorless liquid; .sup.1H NMR (600 MHz, CDCl.sub.3): 7.57 (d, J=9.2 Hz, 2H), 7.51 (d, J=7.9 Hz, 2H), 7.43-7.48 (m, 4H), 7.37-7.29 (m, 4H), 7.26 (d, 3H), 6.43 (d, J=11.7 Hz, 1H), 5.78-5.56 (m, 1H), 3.93-3.53 (m, 1H), 2.66 (t, J=7.1 Hz, 1H), 2.61-2.39 (m, 1H), 0.34 (s, 3H), 0.33 (s, 6H), 0.32 (s, 3H); .sup.13C NMR (150 MHz, CDCl.sub.3): 138.6, 137.6, 137.5, 134.4, 133.8, 133.1, 130.8, 130.1, 129.5, 129.2, 128.9, 128.2, 127.8, 126.6, 67.0, 33.3, 0.8, 0.8, 4.8, 4.8; .sup.29Si NMR (120 MHz, CDCl.sub.3): 6.5, 4.1.

(81) ##STR00060##

(82) (Z)-[1-(Dimethylphenylsilyloxy)-4-(m-tolyl)but-3-en-1-yl]dimethylphenylsilane (reaction time: 2 h, 83%). The compound was prepared from 2-(m-tolyl)furan.

(83) colorless liquid; .sup.1H NMR (600 MHz, CDCl.sub.3): 7.59-7.46 (m, 4H), 7.47-7.29 (m, 6H), 7.19 (t, J=7.6 Hz, 1H), 7.14-7.00 (m, 3H), 6.39 (d, J=11.6 Hz, 1H), 5.75-5.54 (m, 1H), 3.78 (t, J=6.8 Hz, 1H), 2.73-2.59 (m, 1H), 2.59-2.47 (m, 1H), 2.35 (s, 3H), 0.31 (s, 12H); .sup.13C NMR (150 MHz, CDCl.sub.3): 138.5, 137.5, 137.4, 137.3, 134.3, 133.6, 130.5, 130.0, 129.5, 129.3, 129.0, 127.9, 127.6 (2C), 127.2, 125.8, 66.9, 33.1, 21.4, 0.9 (2C), 4.8, 4.9; .sup.29Si NMR (120 MHz, CDCl.sub.3): =6.3, 4.1; HRMS (ESI): Calculated for C27H34NaOSi2 [M+Na]+: 453.2046, Found: 453.2040.

(84) ##STR00061##

(85) (Z)-1-[(Dimethylphenylsilyloxy)-4-(4-phenoxyphenyl)-but-3-en-1-yl]dimethylphenylsilane (reaction time: 1.5 h, 61%). The compound was prepared from 2-(4-phenoxyphenyl)furan.

(86) colorless liquid; .sup.1H NMR (600 MHz, CDCl.sub.3): 7.62 (d, J=6.4 Hz, 2H), 7.57 (d, J=6.4 Hz, 2H), 7.48-7.37 (m, 8H), 7.25 (d, J=8.3 Hz, 2H), 7.20 (t, J=7.4 Hz, 1H), 7.12 (d, J=8.5 Hz, 2H), 7.00 (d, J=8.4 Hz, 2H), 6.44 (d, J=11.5 Hz, 1H), 5.71 (dt, J=11.5, 7.1 Hz, 1H), 3.85 (t, J=6.7 Hz, 1H), 2.76-2.67 (m, 1H), 2.65-2.53 (m, 1H), 0.38 (s, 12H); .sup.13C NMR (150 MHz, CDCl.sub.3): 157.4, 155.8, 138.5, 137.4, 134.4, 133.8, 132.8, 130.3, 130.1, 129.8, 129.5, 129.3, 129.2, 127.8 (2C), 123.3, 118.9, 118.6, 67.0, 33.2, 0.7, 0.8, 4.7, 4.8; .sup.29Si NMR (120 MHz, CDCl.sub.3): 6.5, 4.1; HRMS (EI): Calculated for C32H36O2Si2 [M]+: 508.2254, Found: 508.2256.

(87) ##STR00062##

(88) (Z)-1-[(Dimethylphenylsilyloxy)-4-(4-methylthiophenyl)-but-3-en-1-yl]dimethylphenylsilane (reaction time: 1.5 h, 91%).

(89) colorless liquid; .sup.1H NMR (600 MHz, CDCl.sub.3): 7.51 (d, J=7.6 Hz, 2H), 7.46 (d, J=7.0 Hz, 2H), 7.40-7.27 (m, 6H), 7.19-7.09 (m, 4H), 6.30 (d, J=11.6 Hz, 1H), 5.59 (dt, J=12.1, 7.5 Hz, 1H), 3.73 (t, J=6.6 Hz, 1H), 2.73-2.55 (m, 1H), 2.49 (s, 3H), 2.48-2.43 (m, 1H), 0.27 (s, 12H); .sup.13C NMR (150 MHz, CDCl.sub.3): 138.6, 137.4, 136.4, 134.6, 134.4, 133.8, 130.7, 129.5, 129.4, 129.3, 129.2, 127.8 (2C), 126.5, 66.9, 33.3, 16.1, 0.8, 0.9, 4.8, 4.8; .sup.29Si NMR (120 MHz, CDCl.sub.3): 6.4, 4.1; HRMS (EI): Calculated for C27H34OSSi2 [M]+: 462.1869, Found: 462.1871.

(90) ##STR00063##

(91) (Z)-{1-[(Dimethylphenylsilyl)-4-(dimethylphenylsilyloxy)-but-1-en-1-yl]phenoxy)triisopropylsilane (reaction time: 3 h, 95%).

(92) colorless liquid; .sup.1H NMR (600 MHz, CDCl.sub.3): 7.54 (d, J=6.5 Hz, 2H), 7.50 (d, J=6.5 Hz, 2H), 7.41-7.30 (m, 6H), 7.08 (d, J=8.4 Hz, 2H), 6.80 (d, J=8.5 Hz, 2H), 6.32 (d, J=11.6 Hz, 1H), 5.61-5.45 (m, 1H), 3.79-3.73 (m, 1H), 2.66-2.51 (m, 2H), 1.36-1.25 (m, 3H), 1.15 (d, J=7.4 Hz, 18H), 0.29 (s, 12H); .sup.13C NMR (150 MHz, CDCl.sub.3): 154.8, 138.7, 137.6, 134.4, 133.8, 130.6, 130.0, 129.6, 129.4, 129.2, 128.9, 127.7 (2C), 119.6, 67.1, 33.3, 18.1, 12.9, 0.7, 0.8, 4.8, 4.8; .sup.29Si NMR (120 MHz, CDCl.sub.3): 15.2, 6.3, 4.2; HRMS (EI): Calculated for C35H52O2Si3 [M]+: 588.3275, Found: 588.3279.

(93) ##STR00064##

(94) (Z)-[4-(3,5-Dibromophenyl)-1-(dimethylphenylsilyloxy)but-3-en-1-yl]dimethylphenylsilane (reaction time: 15 h, 79%). The compound was prepared from 2-(3,5-dibromophenyl)furan.

(95) colorless liquid; .sup.1H NMR (600 MHz, CDCl.sub.3): 7.54-7.49 (m, 3H), 7.49-7.44 (m, 2H), 7.43-7.28 (m, 8H), 6.21 (d, J=11.7 Hz, 1H), 5.72-5.67 (m, 1H), 3.75 (dd, J=8.6, 4.9 Hz, 1H), 2.62-2.52 (m, 1H), 2.37-2.27 (m, 1H), 0.29 (s, 6H), 0.28 (s, 6H); .sup.13C NMR (150 MHz, CDCl.sub.3): 140.8, 138.1, 136.9, 134.1, 133.6, 133.6, 131.8, 130.3, 129.4, 129.2, 127.7, 127.6, 127.5, 122.5, 66.4, 32.8, 1.0 (2C), 4.9, 5.0; .sup.29Si NMR (120 MHz, CDCl.sub.3): 6.7, 3.9; HRMS (ESI): Calculated C26H30Br2NaOSi2 [M+Na]+: 595.0100, Found: 595.0095.

(96) ##STR00065##

(97) (Z)-1-[(Dimethylphenylsilyloxy)-4-(2,4,6-triisopropylphenyl)but-3-en-1-yl]dimethylPhenylsilane (reaction time: 6 h, 80%). The compound was prepared from 2-(2,4,6-triisopropylphenyl)furan.

(98) colorless liquid; .sup.1H NMR (600 MHz, CDCl.sub.3): 7.51-7.46 (m, 2H), 7.46-7.41 (m, 2H), 7.40-7.31 (m, 4H), 7.29 (t, J=7.3 Hz, 2H), 7.05-6.90 (m, 2H), 6.28 (d, J=11.6 Hz, 1H), 5.81-5.71 (m, 1H), 3.57 (dd, J=8.9, 5.6 Hz, 1H), 3.12-2.98 (m, 2H), 2.95-2.85 (m, 1H), 2.17-2.09 (m, 1H), 2.08-1.90 (m, 1H), 1.29 (d, J=6.8 Hz, 6H), 1.24-1.13 (m, 4H), 1.13-1.07 (m, 8H), 0.23 (s, 3H), 0.21 (s, 3H), 0.19 (s, 6H); .sup.13C NMR (150 MHz, CDCl.sub.3): 147.4, 138.7, 137.5, 134.3, 133.8, 131.6, 131.1, 129.4, 129.1, 128.2, 127.7, 127.7, 120.3, 120.3, 66.6, 34.4, 33.5, 30.2, 24.5, 24.3, 23.2, 0.9, 1.1, 4.8, 5.0; .sup.29Si NMR (120 MHz, CDCl.sub.3): 5.9, 4.5; HRMS (EI): Calculated for C35H50OSi2 [M]+: 542.3400, Found: 542.3396.

(99) ##STR00066##

(100) (Z)-1-[(Dimethylphenylsilyloxy)-4-(phenanthren-9-yl)but-3-en-1-yl]dimethylphenylsilane (reaction time: 3 h, 82%). The compound was prepared from 2-(phenanthren-9-yl)furan.

(101) colorless liquid; .sup.1H NMR (600 MHz, CDCl.sub.3): 8.84-8.64 (m, 2H), 8.11 (d, 8.0 Hz, 1H), 7.84 (d, J=7.7 Hz, 1H), 7.79-7.66 (m, 4H), 7.66-7.56 (m, 2H), 7.52-7.38 (m, 6H), 7.34 (t, J=6.7 Hz, 1H), 7.26 (t, J=7.3 Hz, 2H), 6.98 (d, J=11.8 Hz, 1H), 6.08 (dt, J=11.6, 7.3 Hz, 1H), 3.87 (dd, J=8.0, 5.3 Hz, 1H), 2.70 (dt, J=15.5, 7.7 Hz, 1H), 2.58-2.49 (m, 1H), 0.4 (s, 6H), 0.34 (s, 3H), 0.31 (s, 3H); .sup.13C NMR (150 MHz, CDCl.sub.3): 138.5, 137.4, 134.3, 133.8, 132.8, 132.7, 131.7, 131.4, 130.5, 130.0, 129.5, 129.1, 128.7, 128.3, 127.8, 127.7, 127.2, 126.7, 126.6, 126.5, 126.4, 125.7, 123.0, 122.5, 67.0, 33.5, 0.8, 0.9, 4.7, 4.8; .sup.29Si NMR (120 MHz, CDCl.sub.3): 6.4, 4.3; HRMS (EI): Calculated for C34H36OSi2 [M]+: 516.2305, Found: 516.2307.

(102) ##STR00067##

(103) (Z)-1,4-Bis[4-(dimethylphenylsilyl)-4-(dimethylphenylsilyloxy)but-1-en-1-yl]benzene (reaction time: 2 h, 72%). The compound was prepared from 1,4-di(furan-2-yl) benzene using dimethylphenylsilane (4.0 equiv.).

(104) colorless liquid; .sup.1H NMR (600 MHz, CDCl.sub.3): 7.54 (d, J=6.4 Hz, 4H), 7.49 (d, J=7.8 Hz, 4H), 7.41-7.35 (m, 8H), 7.33-7.28 (m, 4H), 6.36 (d, J=11.7 Hz, 2H), 5.84-5.53 (m, 2H), 3.86-3.71 (m, 2H), 2.76-2.61 (m, 2H), 2.58-2.49 (m, 2H), 0.30 (s, 24H); .sup.13C NMR (150 MHz, CDCl.sub.3): 138.6, 137.5, 135.8, 134.4, 133.8, 130.6, 129.8, 129.5, 129.2, 128.6, 127.8, 67.0, 33.4, 0.7, 0.8, 4.8, 4.8; .sup.29Si NMR (120 MHz, CDCl.sub.3): 6.4, 4.1; HRMS (EI): Calculated for C46H58O2Si4 [M]+: 754.3514, Found: 754.3517.

(105) ##STR00068##

(106) (3Z,3Z-{[(5-Bromo-1,3-phenylene)bis1-(dimethylphenylsilyloxy)but-3-ene-4,1-diyl]bis(dimethylphenylsilane) (reaction time: 8 h, 81%). The compound was prepared from 2,2-(5-bromo-1,3-phenylene)difuran. B(C6F5)3(4.0 mol %) and dimethylphenylsilane (4.0 equiv.) were used.

(107) colorless liquid; .sup.1H NMR (600 MHz, CDCl.sub.3): 7.53 (d, J=7.2 Hz, 4H), 7.48 (d, J=7.1 Hz, 4H), 7.42-7.29 (m, 14H), 6.95 (s, 1H), 6.26 (d, J=11.7 Hz, 2H), 5.76-5.55 (m, 2H), 3.76 (t, J=6.7 Hz, 2H), 2.71-2.53 (m, 2H), 2.46-2.38 (m, 2H), 0.29 (s, 24H); .sup.13C NMR (150 MHz, CDCl.sub.3): 139.1, 138.3, 137.1, 134.2, 133.6, 132.0, 129.5, 129.4, 129.1, 128.7, 127.9, 127.7, 127.6, 121.8, 66.6, 33.0, 0.94, 0.97, 4.8, 4.9; .sup.29Si NMR (120 MHz, CDCl.sub.3): 6.5, 4.1; HRMS (ESI): Calculated for C46H57BrNaO2Si4 [M+Na]+: 855.2517, Found: 855.2498.

(108) ##STR00069##

(109) (Z)-1,3,5-Tris[4-(dimethylphenylsilyl)-4-(dimethylphenylsilyloxy)but-1-en-1-yl]benzene (reaction time: 2.5 h, 87%). The compound was prepared from 1,3,5-tri(furan-2-yl)benzene. B(C6F5)3(6.0 mol %) and dimethylphenylsilane(6.0 equiv.) were used.

(110) colorless liquid; .sup.1H NMR (600 MHz, CDCl.sub.3): 7.58-7.52 (m, 6H), 7.52-7.45 (m, 6H), 7.42-7.28 (m, 18H), 7.01 (s, 3H), 6.33 (d, J=12.5 Hz, 3H), 5.74-5.61 (m, 3H), 3.78 (d, J=6.5 Hz, 3H), 2.72-2.61 (m, 3H), 2.61-2.50 (m, 3H), 0.35-0.25 (m, 36H); .sup.13C NMR (150 MHz, CDCl.sub.3): 138.4, 137.4, 137.1, 134.2, 133.6, 130.5, 129.9, 129.3, 129.1, 127.6, 127.4, 66.8, 33.2, 0.8, 4.6, 4.9; .sup.29Si NMR (120 MHz, CDCl.sub.3): 6.4, 4.2; HRMS (ESI): Calculated for C66H84NaO3Si6 [M+Na]+: 1115.4934, Found: 1115.4914.

Comparative Example 1

(111) Comparative Example 1 was performed in the same way as in Inventive Example 1 above except that 2-methylfuran, PhMe.sub.2SiH, and CD.sub.2Cl.sub.2 were used during a reaction but a catalyst was not used, but an this case, no product was obtained on a .sup.1H NMR (1,1,2,2-tetrachloroethane (TCE)) spectrum.

Comparative Example 2

(112) Comparative Example 2 was performed in the same way as in Inventive Example 1 above except that 2-methylfuran, PhMe.sub.2SiH, and CD.sub.2Cl.sub.2 were used during a reaction like in Comparative Example 1 above but AlCl.sub.3 was used instead of a borane catalyst as a catalyst, but in this case, a product was obtained with a conversion yield of 10% and a yield of <1% (1% or less) on a .sup.1H NMR(1,1,2,2-tetrachloroethane (TCE)) spectrum.

Comparative Example 3

(113) Comparative Example 3 was performed in the same way as in Inventive Example 1 above except that 2-methylfuran, PhMe.sub.2SiH, and CD.sub.2Cl.sub.2 were used during a reaction in Comparative Example 1 above but [Ir(COH)Cl].sub.2 was used instead of a borane catalyst as a catalyst, but in this case, a product was obtained with a conversion yield of 10% and a yield of <1% on a .sup.1H NMR(1,1,2,2-tetrachloroethane (TCE)) spectrum.

Comparative Example 4

(114) Comparative Example 4 was performed in the same way as in Inventive Example 1 above except that 2-methylfuran, PhMe.sub.2SiH, and CD.sub.2Cl.sub.2 were used during a reaction like in Comparative Example 1 above but [Rh(COD)Cl].sub.2 was used instead of a borane catalyst as a catalyst, but in this case, a product was obtained with a conversion yield of 10% and a yield of <1% on a .sup.1H NMR(1,1,2,2-tetrachloroethane (TCE)) spectrum.

Comparative Example 5

(115) Comparative Example 5 was performed in the same way as in Inventive Example 1 above except that 2-methylfuran, PhMe.sub.2SiH, and CD.sub.2Cl.sub.2 were used during a reaction like in Comparative Example 1 above but Pt(0)-1,3-divinyl-1,1,3,3-tetramethyl-disiloxane was used instead of a borane catalyst as catalyst, but in this case, a product was obtained with a conversion yield of 12% and a yield of <1% on a .sup.1H NMR(1,1,2,2-tetrachloroethane (TCE)) spectrum.

Inventive Example 2 General Preparation of (Z)--silyloxyalkenylsilane Derivative (Silyloxyalkenylsilanes)

(116) ##STR00070##

(117) CH.sub.2Cl.sub.2 (0.4-0.8 mL) and B(C.sub.6F.sub.5).sub.3 (0.01 to 0.02 mmol, 2.0 mol %) were put in a dried flask, a silane compound (PhMe.sub.2SiH, 1.025-2.050 mmol) was added thereto and was well stirred and, then, a furan derivative (0.50 to 1.0 mmol) was again added thereto and, then, was stirred at 23 C. for 3 to 12 hours. The reaction mixture was quenched with Et.sub.3N (5.0 to 10.0 mol %), was subjected to vacuum evaporation, and was isolated and purified (to nucleic acid or hexane and ethyl acetate) via silica gel column chromatography to obtain a target product (Z/E>99/1).

(118) The following compound was prepared using the same method as the above.

(119) ##STR00071##

(120) (Z)-1-[(Dimethylphenylsilyloxy)but-2-en-1-yl]dimethylphenylsilane (reaction time: 12 h): The compound was prepared via a reaction between furan (204 mg, 3.00 mmol) and dimethylphenylsilane (838 mg, 6.15 mmol) in the presence of B(C.sub.6F.sub.5).sub.3 (30.6 mg, 2.0 mol %) melted in CH.sub.2Cl.sub.2 (4.0 mL) (746 mg, 73%).

(121) colorless liquid; .sup.1H NMR (600 MHz, CDCl.sub.3): 7.66-67.62 (m, 2H), 7.60-7.52 (m, 2H), 7.45-7.35 (m, 6H), 5.56 (t, J=11.2 Hz, 1H), 5.43-5.32 (m, 1H), 4.52 (d, J=9.9 Hz, 1H), 1.38 (d, J=8.4 Hz, 3H), 0.41 (s, 3H), 0.36 (s, 9H); .sup.13C NMR (150 MHz, CDCl.sub.3): 138.8, 137.2, 134.5, 133.7, 132.3, 129.4, 129.2, 127.7, 127.6, 121.8, 64.5, 13.5, 0.8, 1.0, 5.5, 5.7; .sup.29Si NMR (120 MHz, CDCl.sub.3): 8.2, 4.8; HRMS (EI): Calculated for C20H28OSi2 [M]+: 340.1679, Found: 340.1676.

(122) ##STR00072##

(123) (Z)-[2-(4-tert-Butyl-phenyl)-1-(dimethylphenylsilyloxy)but-2-en-1-yl]dimethylphenylsilane (reaction time: 3 h, 84%). The compound was prepared from 3-[4-(tert-butyl)phenyl]-furan.

(124) colorless liquid; .sup.1H NMR (600 MHz, CDCl.sub.3): 7.53 (d, J=7.2 Hz, 2H), 7.48-7.40 (m, 3H), 7.39-3.34 (m, 3H), 7.30 (t, J=7.3 Hz, 3H), 7.22 (d, J=7.3 Hz, 3H), 5.57 (q, J=7.1 Hz, 1H), 4.79 (s, 1H), 1.88-1.53 (m, 3H), 1.34 (s, 9H), 0.35 (s, 3H), 0.31 (s, 3H), 0.19 (s, 3H), 0.13 (s, 3H); .sup.13C NMR (150 MHz, CDCl.sub.3): 149.3, 141.4, 140.6, 138.2, 137.8, 134.4, 133.9, 129.5, 129.0, 127.9, 127.8, 127.5, 124.6, 124.2, 67.6, 34.5, 31.5, 14.9, 1.0, 1.4, 4.4, 4.6; .sup.29Si NMR (120 MHz, CDCl.sub.3): 8.4, 3.8; HRMS (EI): Calculated for C30H40OSi2 [M]+: 472.2618, Found: 472.2616.

Inventive Example 3 General Preparation of -Silylated Ketone Derivative (-Silylated Ketone)

(125) ##STR00073##

Preparation of 5-(Dimethylphenylsilyl)-3-methylpentan-2-one

(126) 1) CH.sub.2Cl.sub.2 (8.0 mL) and B(C.sub.6F.sub.5).sub.3 (0.102 g, 2.0 mol %) were put in a well dried flask at 0 C., dimethylphenylsilane (2.79 g, 20.5 mmol) was added thereto and was stirred for 2 minutes, 2,3-dimethylfuran (0.96 g, 10.0 mmol) was added again and, then, current temperature was increased, and the resultant was stirred for 1 hour at 23 C. The reaction mixture was quenched with Et.sub.3N (50 mg, 0.5 mmol), was subjected to vacuum evaporation and, then, was used in the following reaction.

(127) 2) THF (5 mL) was added to the reaction mixture in the above step, tetrabutylammonium fluoride (TBAF) (1 M in THF, 20 m1, 20.0 mmol) was slowly added thereto at 0 C., current temperature was increased again, and the resultant was stirred at 23 C. for 2 hours. Water (20 mL) was added to the reaction mixture and the resultant was subject to extraction with ethyl acetate (15 mL3). The collected organic layers were dried with anhydrous Na.sub.2SO.sub.4, were subjected to vacuum evaporation, and were isolated and purified via silica gel column chromatography (ethyl acetate/hexane 1/9) to obtain a target compound (1.71 g, 73% for two steps).

(128) colorless liquid; .sup.1H NMR (600 MHz, CDCl.sub.3): 7.54-7.47 (m, 2H), 7.40-7.30 (m, 3H), 2.53-2.40 (m, 1H), 2.07 (s, 3H), 1.73-1.58 (m, 1H), 1.45-1.32 (m, 1H), 1.06 (d, J=6.9 Hz, 3H), 0.78-0.62 (m, 2H), 0.28 (s, 6H); .sup.13C NMR (150 MHz, CDCl.sub.3): 212.6, 138.8, 133.5, 128.9, 127.8, 49.8, 28.1, 27.2, 15.7, 13.0, 3.19, 3.27; .sup.29Si NMR (120 MHz, CDCl.sub.3): 2.8; HRMS (ESI): Calculated for C14H22NaOSi [M+Na]+: 257.1338, Found: 257.1330.

Inventive Example 4 General Preparation of (Z)-Homoallylsilane Derivative ((Z)-Homoallylsilane)

(129) ##STR00074##

(130) CH.sub.2Cl.sub.2 (0.8 mL) and B(C.sub.6F.sub.5).sub.3 (0.02 mmol, 2.0 mol %) were put in a well dried flask, diphenylsilane (2.0 mmol) was added thereto and was well stirred, furan derivative (1.0 mmol) was added again, current temperature was increased and, then, the resultant was stirred at 23 C. for 1 hour. The reaction mixture was quenched with Et.sub.3N (5 mmol %), was subjected to vacuum evaporation and, then, was isolated and purified (to hexane) via silica gel column chromatography to obtain a target compound (Z/E>99/1).

(131) The following compound was prepared using the same method as the above.

(132) ##STR00075##

(133) (Z)-1-(Hex-4-en-2-yl)-1,1,3,3-tetraphenyldisiloxane (reaction time: 1 h, 81%). The compound was prepared from 2,5-dimethylfuran.

(134) colorless liquid; .sup.1H NMR (600 MHz, CDCl.sub.3): 7.71-7.56 (m, 8H), 7.50-7.30 (m, 12H), 5.73 (s, 1H), 5.55-5.43 (m, 1H), 5.42-5.32 (m, 1H), 2.34 (d, J=11.2 Hz, 1H), 2.00 (d, J=10.1 Hz, 1H), 1.48 (d, J=5.8 Hz, 3H), 1.45-1.33 (m, 1H), 1.05 (d, J=7.2 Hz, 3H); .sup.13C NMR (150 MHz, CDCl.sub.3): 135.6, 135.4, 134.8, 134.5, 130.5, 130.3, 129.8, 128.05, 127.9, 124.5, 28.2, 20.2, 13.5, 12.9; .sup.29Si NMR (120 MHz, CDCl.sup.3): 8.4, 20.6; HRMS (EI): Calculated for C30H32OSi2 [M]+: 464.1992, Found: 464.1994.

Inventive Example 5 General Preparation of Ortho-(-Silylethyl)-Phenol Derivative (Ortho-(-Silylethyl)-Phenols)

(135) ##STR00076##

(136) CH.sub.2Cl.sub.2 (0.4 mL) and B(C.sub.6F.sub.5).sub.3 (0.025 mmol, 5.0 mol %) were put in a well dried flask, dimethylphenylsilane (1.05 to 1.5 mmol) was added thereto and was well stirred and, then, a benzofuran derivative (0.5 mmol) was added again, current temperature was increased, and the resultant was stirred at 23 C. for 3 to 7 hours. K.sub.2CO.sub.3 (138 mg, 1.00 mmol) melted in methanol (2 mL) was added to the reaction mixture and was stirred at 23 C. for 5 to 7 hours. The resultant was filtered with celite to remove a solid, was subjected to vacuum evaporation and, then, was isolated and purified (to hexane/ethyl acetate) via silica gel column chromatography to prepare a target compound.

(137) The following compound was prepared using the same method as the above.

(138) ##STR00077##

(139) 2-[2-(Dimethylphenylsilyl)ethyl]phenol (reaction time: 5 h, 90%).

(140) colorless liquid; .sup.1H NMR (600 MHz, CDCl.sub.3): 7.64-7.52 (m, 2H), 7.45-7.31 (m, 3H), 7.14 (d, J=7.3 Hz, 1H), 7.07 (t, J=8.3 Hz, 1H), 6.88 (t, J=7.7 Hz, 1H), 6.73 (d, J=7.9 Hz, 1H), 4.69 (s, 1H), 2.97-2.41 (m, 2H), 1.29-0.96 (m, 2H), 0.33 (s, 6H); .sup.13C NMR (150 MHz, CDCl.sub.3): 153.3, 139.2, 133.7, 130.9, 129.4, 129.1, 127.9, 127.0, 120.9, 115.3, 24.2, 15.9, 2.9; .sup.29Si NMR (120 MHz, CDCl.sub.3): 2.7; HRMS (EI): Calculated for C16H20OSi [M]+: 256.1283, Found: 256.1286.

(141) ##STR00078##

(142) 2-[2-(Dimethylphenylsilyl)propyl]phenol (reaction time: 3 h, 88%). The compound was prepared from 2-methylbenzofuran.

(143) colorless liquid; .sup.1H NMR (600 MHz, CDCl.sub.3): 7.77-77.56 (m, 2H), 7.51-7.32 (m, 3H), 7.16-7.02 (m, 2H), 6.87 (t, J=6.0 Hz, 1H), 6.75 (d, J=6.0 Hz, 1H), 4.60 (s, 1H), 2.88 (dd, J=12.0, 6.0 Hz, 1H), 2.19 (d, J=12.0 Hz, 1H), 1.56-1.21 (m, 1H), 0.94 (d, J=7.3 Hz, 3H), 0.37 (s, 6H); .sup.13C NMR (150 MHz, CDCl.sub.3): 153.7, 138.4, 134.1, 130.9, 129.1, 127.9, 127.1, 120.5, 115.4, 32.0, 20.3, 13.9, 4.7, 5.2; .sup.29Si NMR (120 MHz, CDCl.sub.3): 0.55; HRMS (EI): Calculated for C17H22OSi [M]+: 270.1440, Found: 270.1440.

(144) ##STR00079##

(145) 2-{2-(Dimethylphenylsilyl)-2-[4-(triisopropylsilyloxy)phenyl]ethyl phenol (reaction time: 7 h, 70%). The compound was prepared from 2-(naphthalen-1-yl)benzofuran.

(146) colorless liquid; .sup.1H NMR (600 MHz, CDCl.sub.3): 7.53-7.44 (m, 2H), 7.41-7.31 (m, 3H), 6.98-6.89 (m, 1H), 6.82-6.75 (m, 3H), 6.74-4 6.68 (m, 2H), 6.66-6.56 (m, 2H), 4.55-4.27 (m, 1H), 3.07 (dd, J=14.7, 3.2 Hz, 1H), 2.96-2.85 (m, 1H), 2.49 (dd, J=11.7, 3.2 Hz, 1H), 1.27-1.18 (m, 3H), 1.14-0.89 (m, 18H), 0.34 (s, 3H), 0.24 (s, 3H); .sup.13C NMR (150 MHz, CDCl.sub.3): 153.5, 137.7, 135.1, 134.3, 130.5, 129.4, 129.3, 129.1, 128.5, 127.8, 127.0, 120.6, 120.1, 115.6, 36.5, 31.0, 18.0, 12.7, 3.8, 4.9; .sup.29Si NMR (120 MHz, CDCl.sub.3): 15.2, 1.8; HRMS (EI): Calculated for C31H44O2Si2 [M]+: 504.2880, Found: 504.2879.

(147) ##STR00080##

(148) 2-[2-(Dimethylphenylsilyl)-2-phenylethyl]phenol (reaction time: 4 h, 79%). The compound was prepared from 2-phenylbenzofuran.

(149) colorless liquid; .sup.1H NMR (600 MHz, CDCl.sub.3): 7.57-7.49 (m, 2H), 7.47-7.32 (m, 3H), 7.19 (t, J=6.7 Hz, 2H), 7.09 (t, J=7.3 Hz, 1H), 7.04-7.90 (m, 3H), 6.85 (d, J=7.4 Hz, 1H), 6.69 (t, J=6.9 Hz, 1H), 6.62 (d, J=7.9 Hz, 1H), 4.47 (s, 1H), 3.11 (d, J=14.4 Hz, 1H), 3.03 (t, J=13.0 Hz, 1H), 2.66 (d, J=10.6 Hz, 1H), 0.37 (s, 3H), 0.26 (s, 3H); .sup.13C NMR (150 MHz, CDCl.sub.3): 153.5, 142.7, 137.5, 134.3, 130.4, 129.3, 128.3, 128.3, 128.2, 127.9, 127.1, 125.0, 120.6, 115.5, 37.2, 30.5, 3.7, 5.1; .sup.29Si NMR (120 MHz, CDCl.sub.3): 1.3; HRMS (EI): Calculated for C22H24OSi [M]+: 332.1596, Found: 332.159.

Inventive Example 6 Example 1 of Application of the Silane Derivative According to the Present Invention

(150) ##STR00081##

(151) Preparation of (Z)-1-(Dimethylphenylsilyl)pent-3-en-1-ol (reaction time: 4 h, 90%). The compound was prepared from K2CO3 (2.76 g, 20 mmol), MeOH (40 mL), and Z-2 (3.54 g, 10.0 mmol).

(152) colorless liquid; .sup.1H NMR (600 MHz, CDCl.sub.3): 7.65-7.55 (m, 2H), 7.43-7.34 (m, 3H), 5.75-5.57 (m, 1H), 5.49-5.31 (m, 1H), 3.49 (dd, J=12, 6.0 Hz, 1H), 2.49-2.33 (m, 1H), 2.26-2.07 (d, J=14.4 Hz, 1H), 1.61 (d, J=6.7 Hz, 3H), 1.53-1.33 (m, S1 31H), 0.39 (s, 3H), 0.37 (s, 3H); .sup.13C NMR (150 MHz, CDCl.sub.3): 136.9, 134.2, 129.4, 127.9, 127.6, 127.5, 64.6, 31.1, 13.1, 5.3, 5.3; .sup.29Si NMR (120 MHz, CDCl.sub.3): 3.8; HRMS (EI): Calculated for C13H20OSi [M]+: 220.1283, Found: 220.1279.

(153) ##STR00082##

Preparation of (Z)-1-[(Dimethylphenylsilyl)(pent-3-en-1-yl)]-3,5-dinitrobenzoate

(154) (Z-2, 83%). Z-2 (1.00 g, 4.54 mmol) and CH.sub.2Cl.sub.2 (40 mL) were put in a well dried flask, triethylamine (Et.sub.3N) (2.3 g, 22.7 mmol), dimethylaminopyridine (DMAP) (0.910 mmol, 111 mg, 20.0 mol %), and 3,5-dinitrobenzoylchloride (1.36 g, 5.9 mmol) were slowly added thereto at 0 C., and were stirred at 23 C. for 16 hours. The reaction mixture was diluted with CH.sub.2Cl.sub.2, was quenched with water (5 mL), was extracted with CH.sub.2Cl.sub.2 and, then, was washed with salt water. An organic layer was dried with Mg.sub.2SO.sub.4, was subjected to vacuum evaporation and, then, was isolated and purified (to ethyl acetate/hexane 1/10) via silica gel column chromatography to obtain a target compound Z-2 (1.553 g, 83%). The resultant was re-crystallized with CH.sub.2Cl.sub.2 and n-pentane to obtain a compound of yellow crystals.

(155) m.p. 79-81 C.; .sup.1H NMR (600 MHz, CDCl.sub.3): 9.19 (s, 1H), 9.02 (s, 2H), 7.57 (s, 2H), 7.38 (s, 3H), 5.53-5.44 (m, 1H), 5.37-5.32 (m, 1H), 5.31-5.26 (m, 1H), 2.71-2.55 (m, 1H), 2.46-2.28 (m, 1H), 1.54 (d, J=6.6 Hz, 3H), 0.45 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 162.7, 148.8, 135.0, 134.5, 134.1, 130.0, 129.3, 128.2, 126.9, 126.3, 122.2, 71.6, 28.8, 13.0, 4.7, 4.8; .sup.29Si NMR (120 MHz, CDCl.sub.3): 2.6; HRMS (EI): Calculated for C20H22N2O6Si [M]+: 414.1247, Found: 414.1244.

Inventive Example 7 Example 2 of Application of Silane Derivative According to the Present Invention

(156) ##STR00083##

(157) In a light-blocked container, (dimethylphenylsilyl)pent-3-en-1-ol (Z-2, 0.22 g, 1.0 mmol) was melted in benzene (14 mL) and Pb(OAc).sub.4 (0.488 g, 1.1 mmol) was added at 0 C. and under nitrogen gas. The resultant was filtered after a reaction at 23 C. for 2 hours to remove a solid, was subjected to vacuum evaporation, and was isolated and purified (to hexane/ethylacetate 9/1) via silica gel column chromatography to obtain a colorless liquid compound (Z-55).

(158) colorless liquid (0.209 g, 75%); .sup.1H NMR (600 MHz, CDCl.sub.3): 7.59 (d, J=1.6 Hz, 1H), 7.58 (d, J=1.7 Hz, 1H), 7.40-7.34 (m, 3H), 6.00 (t, J=5.3 Hz, 1H), 5.64-5.54 (m, 1H), 5.40-5.30 (m, 1H), 2.48-2.34 (m, 2H), 1.91 (s, 3H), 1.58 (d, J=6.9 Hz, 3H), 0.44 (s, 3H), 0.43 (s, 3H); .sup.13C NMR (150 MHz, CDCl.sub.3): 169.9, 137.0, 133.5, 129.7, 127.7, 127.5, 123.2, 92.1, 34.4, 21.1, 12.9, 1.4; .sup.29Si NMR (120 MHz, CDCl.sub.3): 8.8; IR (cm.sup.1): 2958, 1737, 1590, 1427, 1370, 1238, 1117, 1007, 935, 823, 699; HRMS (ESI): Calculated for C15H22NaO3Si [M+Na]+: 301.1236, Found: 301.1230

Inventive Example 8 Example 3 of Application of Silane Derivative According to the Present Invention

(159) ##STR00084##

Preparation of (Z)-2-[1-(Dimethylphenylsilyl)pent-3-en-1-yl]isoindoline-1,3-dione (Z-56)

(160) (Z)-1-(dimethylphenylsilyl)pent-3-en-1-ol (Z-2, 0.22 g, 1.0 mmol), triphenylphosphine (TPP, 0.34 g, 1.3 mmol), and phthalimide (0.191 g, 1.3 mmol) were melted in THF (2.0 mL), diethyl azodicarboxylate (DEAD, 226 g, 1.3 mmol) was slowly added thereto at 0 C. under nitrogen gas, and was stirred at 23 C. for 20 hours. The reaction mixture was subjected to vacuum evaporation and was isolated and purified (to hexane/ethyl acetate 9/1) via silica gel column chromatography to obtain a colorless and viscous liquid Z-56.

(161) colorless viscous oil (0.265 g, 76%). .sup.1H NMR (600 MHz, CDCl.sub.3): 7.79-7.72 (m, 2H), 7.68-7.61 (m, 2H), 7.60-7.53 (m, 2H), 7.35-7.29 (m, 3H), 5.49-5.34 (m, 1H), 5.34-5.18 (m, 1H), 4.03 (dd, J=11.6, 4.5 Hz, 1H), 2.99-2.83 (m, 1H), 2.41-2.25 (m, 1H), 1.6 (d, J=6.7 Hz, 3H), 0.59 (s, 3H), 0.45 (s, 3H); .sup.13C NMR (100 MHz, CDCl.sub.3): 168.9, 136.8, 133.8, 133.6, 131.9, 129.3, 127.8, 127.5, 126.6, 122.8, 41.1, 26.0, 12.6, 3.3, 3.8; .sup.29Si NMR (80 MHz, CDCl.sub.3): 0.3; IR (cm.sup.1): 2954, 1770, 1705, 1466, 1427, 1385, 1249, 1172, 1078, 985, 882, 717; HRMS (ESI): Calculated for C21H23NNaO2Si [M+Na]+: 372.1396, Found: 372.1383

Inventive Example 9 Example 4 of Application of Silane Derivative According to the Present Invention

(162) ##STR00085##

Preparation of 2-[(4-Bromophenyl)-6-(dimethylphenylsilyl)]-3-methyltetrahydro-2H-pyran-4-ol

(163) (Z)-1-(dimethylphenylsilyl)pent-3-en-1-ol (Z-2, 0.22 g, 1.0 mmol) and 4-bromobenzaldehyde (0.221 g, 1.2 mmol) were melted in CH.sub.2Cl.sub.2 (5 mL), trifluoroacetic acid (0.285 g, 2.25 mmol) was slowly added thereto at 20 C. under nitrogen gas and, then, a reaction was performed at the same temperature for 3 hours. The resultant was quenched with 5 mL of a saturated sodium hydrogen carbonate (NaHCO.sub.3) solution and, then, triethylamine was added thereto to satisfy pH>7. Organic layers collected via extraction with CH.sub.2Cl.sub.2 (35 mL) were dried with anhydrous Na.sub.2SO.sub.4 and were subjected to vacuum evaporation. MeOH (6 mL) was added thereto, K.sub.2CO.sub.3 (0.276 g, 2.0 mmol) was added at 0 C., and a reaction was performed for 2 hours. When the reaction was completed, the resultant was filtered with celite, and was subjected to vacuum evaporation, and was isolated and purified (to hexane/ethyl acetate 7/3) via silica gel column chromatography to obtain a colorless liquid compound 58 (0.230 g, 57% for two steps).

(164) colorless liquid with single diastereomer. .sup.1H NMR (600 MHz, CDCl.sub.3): 7.69-7.58 (m, 2H), 7.47 (d, J=4.9 Hz, 2H), 7.42-7.33 (m, 3H), 7.17 (d, J=5.1 Hz, 2H), 4.41 (d, J=3.4 Hz, 1H), 4.07-4.00 (m, 1H), 3.46 (d, J=13.2 Hz, 1H), 2.21-2.12 (m, 1H), 1.80-1.71 (m, 1H), 1.67 (q, J=13.0 Hz, 1H), 1.60-1.52 (m, 1H), 0.57 (d, J=3.5 Hz, 3H), 0.42 (s, 6H); .sup.13C NMR (150 MHz, CDCl.sub.3): 140.8, 136.4, 134.1, 131.1, 129.3, 127.8, 127.1, 120.2, 81.8, 72.2, 70.0, 40.7, 30.0, 4.9, 5.4, 5.6; .sup.29Si NMR (120 MHz, CDCl.sub.3): 4.7; IR (cm.sup.1): 3369, 2968, 1707, 1589, 1488, 1361, 1247, 1114, 1009, 817, 699; HRMS (ESI): Calculated for C20H25BrNaO2Si [M+Na]+: 427.0705, Found: 427.0688.

(165) ##STR00086##

Preparation of [(4-Bromophenyl)-6-(dimethylphenylsilyl)]-3-methyltetrahydro-2H-pyran-4-yl-3,5-dinitrobenzoate (Compound 58)

(166) Compound 58 (40.4 mg, 0.1 mmol) prepared as described above was melted in CH.sub.2Cl.sub.2 (2 mL), triethylamine (51 mg, 0.3 mmol) and 4-dimethylaminopyridine (DMAP, 0.1 mg, 0.001 mmol, 1 mol %) were added thereto and, then, 3,5-dinitrobenzoyl chloride (28 mg, 0.12 mmol) was slowly added again at 0 C. The reaction mixture was stirred at 23 C. for 12 hours. Water (3 mL) was added to the reaction mixture and was subjected to extraction with CH.sub.2Cl.sub.2 (3 mL3). The collected organic layers were dried with anhydrous Na.sub.2SO.sub.4, were subjected to vacuum evaporation, and were isolated and purified (to hexane/ethyl acetate 8/2) via silica gel chromatography to obtain a single stereoisomer compound 58 (56 mg, 94%). The resultant was re-crystallized with ethyl acetate and hexane to obtain a yellow color solid.

(167) Yellow color solid; m.p. 145-147 C.; .sup.1H NMR (600 MHz, CDCl.sub.3): 9.21 (t, J=2.1 Hz, 1H), 9.11 (d, J=2.1 Hz, 2H), 7.67-7.55 (m, 2H), 7.47 (d, J=8.5 Hz, 2H), 7.43-7.33 (m, 3H), 7.18 (d, J=8.1 Hz, 2H), 5.56-5.46 (m, 1H), 4.59 (d, J=1.4 Hz, 1H), 3.60 (dd, J=13.3, 2.4 Hz, 1H), 2.50-2.44 (m, 1H), 1.99 (td, J=13.0, 11.6 Hz, 1H), 1.79-1.71 (m, 1H), 0.70 (d, J=6.9 Hz, 3H), 0.45 (s, 3H), 0.44 (s, 3H); .sup.13C NMR (150 MHz, CDCl.sub.3): 161.7, 148.6, 139.7, 135.8, 134.1, 134.06, 131.2, 129.5, 129.3, 127.9, 127.0, 122.4, 120.6, 81.6, 77.6, 70.0, 37.9, 26.7, 6.0, 5.4, 5.6; .sup.29Si NMR (120 MHz, CDCl.sub.3): 4.2; IR (cm.sup.1): 3099, 1728, 1628, 1546, 1487, 1343, 1277, 1168, 1047, 906, 783; HRMS (ESI): Calculated for C27H27BrN2NaO7Si [M+Na]+: 621.0669, Found: 621.0684.

(168) The method of preparing a silane derivative via a reaction between a furan derivative and a silane compound in the presence of a borane catalyst according to the present invention may not use transition metal as a catalyst and, thus, may synthesize a silane derivative with a high yield via high stereoselectivity even under an eco-friendly and mild condition, in detail, using low temperature and short reaction time.

(169) Accordingly, the method of preparing a silane derivative according to the present invention may be easily and commercially applied to be mass-produced.

(170) In addition, the silane derivative prepared using the method of preparing a silane derivative according to the present invention may be used as an intermediate of various compounds as described in Inventive Examples 6 to 9 according to the present invention and, thus, may be used as an intermediate or raw material in various ways such as synthesis of medicines and natural products.

II. Preparation of Anti-Cyclopropyl Silane Compound from Furan Compound

Inventive Example 10

Preparation of anti-(2-Ethylcyclopropyl)dimethylphenylsilane (Anti-33)

(171) ##STR00087##

(172) B(C.sub.6F.sub.5).sub.3 (0.025 mmol, 5.0 mol %) was dissolved in CH.sub.2Cl.sub.2 (0.2 mL), dimethylphenylsilane (2.0 mmol) was added thereto and, then, the resultant was stirred. 2-methylfuran (0.50 mmol) was added at 0 C. and the reaction mixture was stirred at 23 C. for 6 hours. Et.sub.3N (5 eq based on B(C.sub.6F.sub.5).sub.3) was added to complete a reaction and, then, was subjected to vacuum evaporation. The evaporated crude product was purified via silica gel flash column chromatography (eluant: hexane or mixture of hexane and ethyl acetate) to obtain anti-(2-Ethylcyclopropyl)dimethylphenylsilane (anti-33) (yield of 83%, dr.>99/1).

(173) Colorless liquid; .sup.1H NMR (600 MHz, CDCl.sub.3): 7.82-7.76 (m, 2H), 7.56-7.52 (m, 3H), 1.69-1.59 (m, 1H), 1.48-1.38 (m, 1H), 1.19 (t, J=7.3 Hz, 3H), 0.92-0.83 (m, 1H), 0.69-0.59 (m, 2H), 0.43 (s, 3H), 0.41 (s, 3H), 0.17-0.30 (m, 1H); .sup.13C NMR (150 MHz, CDCl.sub.3): 139.6, 133.9, 128.9, 127.8, 29.1, 17.8, 14.13, 9.1, 3.4, 3.4, 3.7; .sup.29Si NMR (120 MHz, CDCl.sub.3): 2.9; HRMS (EI): Calculated for C.sub.13H.sub.20Si [M].sup.+: 204.1334, Found: 204.1333.

Inventive Example 11 Preparation of anti-(2-Ethylcyclopropyl)diphenylsilane (Anti-36)

(174) ##STR00088##

(175) Anti-(2-Ethylcyclopropyl)diphenylsilane (anti-36) (yield of 81%, dr.>99/1) was obtained via a reaction between 2-methylfuran (164 mg, 2.0 mmol) and diphenylsilane (1.11 g, 6.0 mmol) for 4 hours using B(C.sub.6F.sub.5).sub.3 (51 mg, 5.0 mol %) dissolved in CH.sub.2Cl.sub.2 (1.0 mL) in the same method as Inventive Example 10.

(176) colorless liquid; .sup.1H NMR (600 MHz, CDCl.sub.3): 7.69 (d, J=6.9 Hz, 4H), 7.51-7.39 (m, 6H), 4.79 (d, J=3.8 Hz, 1H), 1.50-1.27 (m, 2H), 1.07 (t, J=7.3 Hz, 3H), 0.91-0.80 (m, 1H), 0.71-0.49 (m, 2H), 0.03-0.18 (m, 1H); .sup.13C NMR (150 MHz, CDCl.sub.3): 135.5, 134.6, 129.7, 127.9, 28.8, 18.6, 13.9, 9.7, 0.12; .sup.29Si NMR (120 MHz, CDCl.sub.3): 10.7; HRMS (EI): Calculated for C.sub.17H.sub.20Si [M].sup.+: 252.1334, Found 252.1336.

Inventive Example 12 Preparation of Anti-(2-Propylcyclopropyl)dimethylphenylsilane (Anti-37)

(177) ##STR00089##

(178) Anti-(2-Propylcyclopropyl)dimethylphenylsilane (anti-37) (yield of 77%, dr.>99/1) was obtained via a reaction for 5 hours using the same method as Inventive Example 10 above except that 2-ethylfuran was used instead of 2-methylfuran.

(179) colorless liquid; .sup.1H NMR (600 MHz, CDCl.sub.3): 7.72-7.62 (m, 2H), 7.49-7.40 (m, 3H), 1.57-1.41 (m, 3H), 1.35-1.20 (m, 1H), 1.07-0.94 (m, 3H), 0.84-0.73 (m, 1H), 0.58-0.43 (m, 2H), 0.30 (s, 3H), 0.28 (s, 3H), 0.30-0.41 (m, 1H); .sup.13C NMR (150 MHz, CDCl.sub.3): 139.7, 133.9, 128.9, 127.8, 38.3, 23.1, 15.7, 14.2, 9.2, 3.4, 3.4, 3.7; .sup.29Si NMR (120 MHz, CDCl.sub.3): 2.9; HRMS (EI): Calculated for C.sub.14H.sub.22Si [M].sup.+: 218.1491, Found 218.1495.

Inventive Example 13 Preparation of anti-(2-Butylcyclopropyl)dimethylphenylsilane (Anti-38)

(180) ##STR00090##

(181) Anti-(2-Butylcyclopropyl)dimethylphenylsilane (anti-38) (yield of 66%, dr.>99/1) was obtained via a reaction for 5 hours using the same method as Inventive Example 10 except that 2-propylfuran was used instead of 2-methylfuran.

(182) colorless liquid; .sup.1H NMR (600 MHz, CDCl.sub.3): 7.67-7.56 (m, 2H), 7.48-7.29 (m, 3H), 1.47-1.31 (m, 5H), 1.28-1.17 (m, 1H), 0.97-0.90 (m, 3H), 0.79-0.59 (m, 1H), 0.52-0.38 (m, 2H), 0.25 (s, 3H), 0.22 (s, 3H), 0.33-0.49 (m, 1H); .sup.13C NMR (150 MHz, CDCl.sub.3): 139.7, 133.9, 128.9, 127.8, 35.8, 32.3, 22.7, 15.9, 14.3, 9.3, 3.5, 3.5, 3.7; .sup.29Si NMR (120 MHz, CDCl.sub.3): 2.9; HRMS (EI): Calculated for C.sub.15H.sub.24Si [M]+: 232.1647, Found: 232.1646.

Inventive Example 14 Preparation of anti-(2-Hexcyclopropyl)dimethylphenylsilane (Anti-39)

(183) ##STR00091##

(184) Anti-(2-Hexcyclopropyl)dimethylphenylsilane (anti-39) (yield of 83%, dr.>99/1) was obtained via a reaction using the same method as Inventive Example 10 above except that 2-pentylfuran was used instead of 2-methylfuran.

(185) colorless liquid; .sup.1H NMR (600 MHz, CDCl.sub.3): 7.73-7.53 (m, 2H), 7.36-7.01 (m, 3H), 1.42-1.04 (m, 10H), 0.91-0.77 (m, 3H), 0.70-0.58 (m, 1H), 0.49-0.29 (m, 2H), 0.16 (s, 3H), 0.14 (s, 3H), 0.45-0.55 (m, 1H); .sup.13C NMR (150 MHz, CDCl.sub.3): 139.3, 133.5, 128.5, 127.4, 76.8, 35.7, 31.8, 29.6, 29.0, 22.5, 15.6, 13.9, 8.9, 3.1, 3.8, 4.1; .sup.29Si NMR (120 MHz, CDCl.sub.3): 2.9; HRMS (EI): Calculated for C.sub.17H.sub.23Si [M].sup.+: 260.1960, Found: 260.1962.

Inventive Example 15 Preparation of anti-2-{2-[(1,1-Biphenyl-4-yl)ethyl]cyclopropyl}dimethylphenylsilane (Anti-40)

(186) ##STR00092##

(187) B(C.sub.6F.sub.5).sub.3 (0.025 mmol, 5.0 mol %) was dissolved in CH.sub.2Cl.sub.2 (0.2 mL), dimethylphenylsilane (2.0 mmol) was added thereto, and the resultant was stirred. 2-[(1,1-biphenyl)-4-ylmethyl]furan (1ac, 0.50 mmol) was added at 0 C. and the reaction mixture was stirred at 23 C. for 6 hours. Et.sub.3N (5 eq based on B(C.sub.6F.sub.5).sub.3) was added thereto to complete a reaction.

(188) Then, the resultant was subjected to vacuum evaporation, was diluted with THF (0.5 ml) and, then, was cooled to 0 C., and tetrabutylammonium fluoride (TBAF) (1 M in THF, 3.0 mL) was slowly applied thereto and, then, was stirred at 55 C. After 12 hours elapsed, the resultant was cooled to 23 C., water (5 mL) was added thereto to complete a reaction and, then, the resultant was subjected to extraction with ethyl acetate (5 mL3). The obtained organic layer was subjected to vacuum evaporation. The evaporated crude product was purified via silica gel flash column chromatography (eluant: hexane or mixture of hexane and ethyl acetate) to obtain anti-2-{2-[(1,1-Biphenyl-4-yl)ethyl]cyclopropyl}dimethylphenylsilane (anti-40) (yield of 74%, dr.>99/1).

(189) colorless liquid; .sup.1H NMR (600 MHz, CDCl.sub.3): 7.71 (t, J=7.0 Hz, 4H), 7.63 (d, J=8.0 Hz, 2H), 7.54 (t, J=7.6 Hz, 2H), 7.50-7.46 (m, 3H), 7.44 (t, J=6.9 Hz, 1H), 7.35 (d, J=7.9 Hz, 2H), 2.92-2.81 (m, 2H), 1.93-1.84 (m, 1H), 1.73-1.62 (m, 1H), 0.94-0.82 (m, 1H), 0.67-0.52 (m, 2H), 0.35 (s, 3H), 0.33 (s, 3H), 0.19-0.28 (m, 1H); .sup.13C NMR (150 MHz, CDCl.sub.3): 141.8, 141.3, 139.4, 138.7, 133.9, 128.9, 128.9, 128.8, 127.8, 127.1, 38.0, 35.9, 15.9, 9.3, 3.9, 3.5, 3.6; .sup.29Si NMR (120 MHz, CDCl.sub.3): 2.9; HRMS (ESI): Calculated for C.sub.25H.sub.28NaSi [M+Na].sup.+: 379.1858, Found: 379.1852.

Inventive Example 16 Preparation of anti-{2-[4-(Trifluoromethyl)benzyl]cyclopropyl}dimethylphenylsilane (Anti-41)

(190) ##STR00093##

(191) Anti-{2-[4-(Trifluoromethyl)benzyl]cyclopropyl}dimethylphenylsilane (anti-41) (yield of 80%, dr.>99/1) was obtained via a reaction using the same method as Inventive Example 15 except that 2-[4-(trifluoromethyl)phenyl]-furan (1e) was used instead of 2-[(1,1-biphenyl)-4-ylmethyl]furan (1ac).

(192) colorless liquid; .sup.1H NMR (600 MHz, CDCl.sub.3): 7.54 (d, J=7.8 Hz, 2H), 7.48 (d, J=6.9 Hz, 2H), 7.39 (d, J=9.9 Hz, 1H), 7.34 (t, J=7.1 Hz, 4H), 2.82 (dd, J=14.7, 6.3 Hz, 1H), 2.59 (dd, J=14.6, 7.1 Hz, 1H), 1.04-0.94 (m, 1H), 0.68-0.56 (m, 2H), 0.22 (s, 3H), 0.17 (s, 3H), 0.13-0.31 (m, 1H); .sup.13C NMR (150 MHz, CDCl.sub.3): 146.2, 139.0, 133.8, 129.1, 128.8, 127.8, 126.2, 125.3 (q, J=3.7 Hz), 124. (q, J=273 Hz), 41.5, 16.8, 9.3, 3.9, 3.6, 3.9; .sup.29Si NMR (120 MHz, CDCl.sub.3): 2.9; .sup.19F NMR (CDCl.sub.3, 375 MHz): 62.3; HRMS (EI): Calculated for (C.sub.19H.sub.21F.sub.3Si [M].sup.+: 334.1365, Found: 334.1367.

Inventive Example 17 Preparation of anti-[(4-Fluorobenzyl)cyclopropyl]dimethylphenylsilane (Anti-42)

(193) ##STR00094##

(194) Anti-[(4-Fluorobenzyl)cyclopropyl]dimethylphenylsilane (anti-42) (yield of 64%, dr.>99/1) was obtained using the same method as Inventive Example 15 except that 2-(4-fluorophenyl) furan (1f) was used instead of 2-[(1,1-biphenyl)-4-ylmethyl]furan (1ac).

(195) Colorless liquid; .sup.1H NMR (600 MHz, CDCl.sub.3): 7.44 (d, J=6.0 Hz, 2H), 7.39-7.30 (m, 3H), 7.22-7.13 (m, 2H), 7.02-6.92 (m, 2H), 2.70 (dd, J=14.3, 6.7 Hz, 1H), 2.50 (dd, J=14.4, 7.0 Hz, 1H), 0.98-0.91 (m, 1H), 0.64-0.52 (m, 2H), 0.17 (s, 3H), 0.14 (s, 3H), 0.12-0.32 (m, 1H); .sup.13C NMR (150 MHz, CDCl.sub.3): 161.5 (d, J=243.2 Hz), 139.18, 137.79-137.62 (d J=3.0 Hz), 133.86, 129.01, 129.82 (d, J=7.8 Hz), 127.81, 115.05 (d, J=21.0 Hz), 40.87, 17.15, 9.26, 3.73, 3.64, 3.76; .sup.29Si NMR (120 MHz, CDCl.sub.3): 2.9; .sup.19F NMR (CDCl.sub.3, 375 MHz): 117.9; HRMS (EI): Calculated for C.sub.13H.sub.21FSi [M].sup.+: 284.1397, Found: 284.1399.

Inventive Example 18 Preparation of anti-2-[(4-Chlorobenzyl)cyclopropyl]dimethylphenylsilane (Anti-43)

(196) ##STR00095##

(197) Anti-2-[(4-Chlorobenzyl)cyclopropyl]dimethylphenylsilane (anti-43) (yield of 80%, dr.>99/1) was obtained via a reaction using the same method as Inventive Example 15 except that 2-(4-chlorophenyl)furan (1g) was used instead of 2-[(1,1-biphenyl)-4-ylmethyl]furan (1ac).

(198) Colorless liquid; .sup.1H NMR (600 MHz, CDCl.sub.3): 7.48 (d, J=7.5 Hz, 2H), 7.41-7.30 (m, 3H), 7.24 (d, J=7.5 Hz, 2H), 7.15 (d, J=7.9 Hz, 2H), 2.72 (dd, J=14.5, 6.3 Hz, 1H), 2.51 (dd, J=14.5, 7.0 Hz, 1H), 1.00-0.91 (m, 1H), 0.66-0.53 (m, 2H), 0.20 (s, 3H), 0.16 (s, 3H), 0.17-0.29 (m, 1H); .sup.13C NMR (150 MHz, CDCl.sub.3): 140.5, 139.1, 133.8, 131.7, 129.9, 129.0, 128.4, 127.8, 41.0, 16.9, 9.3, 3.8, 3.6, 3.8; .sup.29Si NMR (120 MHz, CDCl.sub.3): 2.9; HRMS (EI): Calculated for C.sub.18H.sub.21ClSi [M].sup.+: 300.1101, Found: 300.1097.

Inventive Example 19 Preparation of anti-2-[(4-Bromobenzyl)cyclopropyl]dimethylphenylsilane (Anti-44)

(199) ##STR00096##

(200) Anti-2-[(4-Bromobenzyl)cyclopropyl]dimethylphenylsilane (anti-44) (yield of 71%, dr.>99/1) was obtained via a reaction using the same method as Inventive Example 15 except that 2-(4-bromophenyl)-furan (1h) was used instead of 2-[(1,1-biphenyl)-4-ylmethyl]furan (1ac).

(201) Colorless liquid; .sup.1H NMR (600 MHz, CDCl.sub.3): 7.49 (d, J=6.4 Hz, 2H), 7.43-7.38 (m, 3H), 7.35 (t, J=7.0 Hz, 2H), 7.11 (d, J=8.3 Hz, 2H), 2.71 (dd, J=14.6, 6.4 Hz, 1H), 2.50 (dd, J=14.6, 7.0 Hz, 1H), 1.07-0.89 (m, 1H), 0.68-0.54 (m, 2H), 0.21 (s, 3H), 0.17 (s, 3H), 0.15-0.31 (m, 1H); .sup.13C NMR (150 MHz, CDCl.sub.3): 141.0, 139.1, 133.8, 131.4, 130.3, 129.0, 127.8, 119.8, 41.1, 16.9, 9.3, 3.8, 3.6, 3.8; .sup.29Si NMR (120 MHz, CDCl.sub.3): 2.9; HRMS (EI): Calculated for C.sub.18H.sub.21BrSi [M].sup.+: 344.0596, Found: 344.0592.

Inventive Example 20 Preparation of anti-2-{[(1,1-Biphenyl)-4-ylmethyl]cyclopropyl}dimethylphenylsilane (Anti-45)

(202) ##STR00097##

(203) Anti-2-{[(1,1-Biphenyl)-4-ylmethyl]cyclopropyl}dimethylphenylsilane (anti-45) (yield of 85%, dr.>99/1) was obtained using the same method as Inventive Example 10 except that 2-(1,1-biphenyl-4-yl)furan (1i) was added instead of 2-methylfuran at 78 C. and was subjected to a reaction at 40 C. for 10 hours.

(204) Colorless liquid; .sup.1H NMR (600 MHz, CDCl.sub.3): 7.65 (d, J=7.6 Hz, 2H), 7.58-7.51 (m, 4H), 7.49 (t, J=7.8 Hz, 2H), 7.43-7.28 (m, 6H), 2.85-2.73 (m, 1H), 2.70-2.58 (m, 1H), 1.07 (q, J=5.8 Hz, 1H), 0.71-0.58 (m, 2H), 0.24 (s, 3H), 0.21 (s, 3H), 0.11-0.29 (m, 1H)); .sup.13C NMR (150 MHz, CDCl.sub.3): 141.2, 141.1, 139.1, 138.8, 133.8, 128.8, 128.7, 127.7, 127.04, 127.02, 41.2, 16.9, 9.2, 3.6, 3.6, 3.7; .sup.29Si NMR (120 MHz, CDCl.sub.3): 2.8; HRMS (EI): Calculated for C.sub.24H.sub.26Si [M].sup.+: 342.1804, Found: 342.1801.

Inventive Example 21 Preparation of anti-2-{[(4-Methylthio)benzyl]cyclopropyl}dimethylphenylsilane (Anti-46)

(205) ##STR00098##

(206) Anti-2-{[(4-Methylthio)benzyl]cyclopropyl}dimethylphenylsilane (anti-46) (yield of 90%, dr.>99/1) was obtained via a reaction using the same method as Inventive Example 10 except that 2-[4-(methylthio)phenyl]furan (1 m) was used instead of 2-methylfuran.

(207) Colorless liquid; .sup.1H NMR (600 MHz, CDCl.sub.3): 7.53 (d, J=7.0 Hz, 2H), 7.41-7.36 (m, 3H), 7.25 (d, J=8.0 Hz, 2H), 7.20 (d, J=8.1 Hz, 2H), 2.74 (dd, J=14.5, 6.4 Hz, 1H), 2.58 (dd, J=14.5, 6.9 Hz, 1H), 2.53 (s, 3H), 1.07-0.99 (m, 1H), 0.66-0.58 (m, 2H), 0.24 (s, 3H), 0.21 (s, 3H), 0.14-0.24 (m, 1H); .sup.13C NMR (150 MHz, CDCl.sub.3): 139.3, 135.5, 133.9, 129.1, 127.8, 127.3, 41.1, 17.0, 16.54, 9.2, 3.7, 3.6, 3.7; .sup.29Si NMR (120 MHz, CDCl.sub.3): 2.9; HRMS (EI): Calculated for C.sub.19H.sub.24SSi [M].sup.+: 312.1368, Found: 312.1366.

Inventive Example 22 Preparation of anti-[2-(3-Methylbenzyl)cyclopropyl]dimethylphenylsilane (Anti-47)

(208) ##STR00099##

(209) Anti-[2-(3-Methylbenzyl)cyclopropyl]dimethylphenylsilane (anti-47) (yield of 83%, dr.>99/1) was obtained using the same method as Inventive Example 15 except that 2-(m-tolyl)furan (1k) was added instead of 2-[(1,1-biphenyl)-4-ylmethyl]furan (1ac) at 78 C.

(210) Colorless liquid; .sup.1H NMR (600 MHz, CDCl.sub.3): 7.50 (d, J=7.8 Hz, 2H), 7.39-7.30 (m, 3H), 7.18 (t, J=7.5 Hz, 1H), 7.06 (s, 1H), 7.05-7.01 (m, 2H), 2.69-2.63 (m, 1H), 2.61-2.49 (m, 1H), 2.34 (s, 3H), 1.05-0.89 (m, 1H), 0.61-0.52 (m, 2H), 0.18 (s, 3H), 0.16 (s, 3H), 0.16-0.30 (m1H); .sup.13C NMR (150 MHz, CDCl.sub.3): 141.9, 139.2, 137.7, 133.7, 129.1, 128.8, 128.1, 127.6, 126.6, 125.4, 41.5, 21.4, 16.8, 9.1, 3.5, 3.7, 3.8; .sup.29Si NMR (120 MHz, CDCl.sub.3): 2.9; HRMS (EI): Calculated for C.sub.19H.sub.24Si [M].sup.+: 280.1647, Found: 280.1648.

Inventive Example 23 Preparation of anti-[2-(3,5-Dibromobenzyl)cyclopropyl]dimethylphenylsilane (Anti-48)

(211) ##STR00100##

(212) Anti-[2-(3,5-Dibromobenzyl)cyclopropyl]dimethylphenylsilane (anti-48) (yield of 81%, dr.>99/1) was obtained using the same method as Inventive Example 10 except that 2-(3,5-dibromophenyl)furan (1o) was added instead of 2-methylfuran at 78 C. and was subjected to a reaction at 40 C. for 22 hours.

(213) Colorless liquid; .sup.1H NMR (600 MHz, CDCl.sub.3): 7.58-7.47 (m, 3H), 7.43-7.36 (m, 3H), 7.34 (s, 2H), 2.72-2.64 (m, 1H), 2.52-2.43 (m, 1H), 1.00-0.87 (m, 1H), 0.64-0.54 (m, 2H), 0.22 (s, 3H), 0.21 (s, 3H), 0.18-0.27 (m, 1H); .sup.13C NMR (150 MHz, CDCl.sub.3): 146.0, 138.6, 133.7, 131.6, 130.1, 129.0, 127.7, 122.7, 40.9, 16.4, 9.3, 3.9, 3.6, 3.8; .sup.29Si NMR (120 MHz, CDCl.sub.3): 2.9.

Inventive Example 24 Preparation of anti-[2-(2,4,6-Triisopropylbenzyl)cyclopropyl]dimethylphenylsilane (Anti-49)

(214) ##STR00101##

(215) Anti-[2-(2,4,6-Triisopropylbenzyl)cyclopropyl]dimethylphenylsilane (anti-49) (yield of 77%, dr.>99/1) was obtained via a reaction using the same method as Inventive Example 15 except that 2-(2,4,6-triisopropylphenyl)furan (1p) was used instead of 2-[(1,1-biphenyl)-4-ylmethyl]furan (1ac).

(216) colorless liquid; .sup.1H NMR (600 MHz, CDCl.sub.3): 7.57 (d, J=7.3 Hz, 2H), 7.45-7.33 (m, 3H), 7.06 (s, 2H), 3.35-3.26 (m, 2H), 3.02 (dd, J=14.5, 4.2 Hz, 1H), 2.99-2.91 (m, 1H), 2.77 (dd, J=14.5, 6.3 Hz, 1H), 1.35 (s, 3H), 1.34 (s, 3H), 1.30 (s, 6H), 1.29 (s, 6H), 0.96-0.87 (m, 1H), 0.67-0.60 (m, 1H), 0.57-0.51 (m, 1H), 0.27 (s, 3H), 0.23 (s, 3H), 0.17-0.29 (m, 1H); .sup.13C NMR (150 MHz, CDCl.sub.3): 147.0, 146.4, 139.3, 133.9, 131.9, 128.9, 127.8, 120.9, 34.3, 30.9, 29.5, 24.7, 24.4, 24.3, 16.8, 9.4, 2.6, 3.7; .sup.29Si NMR (120 MHz, CDCl.sub.3): 2.7; HRMS (EI): Calculated for C.sub.27H.sub.40Si [M].sup.+: 392.2899, Found: 392.2898.

Inventive Example 25 Preparation of anti-[2-(Phenanthren-9-ylmethyl)cyclopropyl]dimethylphenylsilane (anti-50)

(217) ##STR00102##

(218) Anti-[2-(Phenanthren-9-ylmethyl)cyclopropyl]dimethylphenylsilane (anti-50) (yield of 81%, dr.>99/1) was obtained via a reaction for 10 hours using the same method as Inventive Example 10 except that 2-(phenanthren-9-yl)furan (1q) was used instead of 2-methylfuran.

(219) Colorless liquid; .sup.1H NMR (600 MHz, CDCl.sub.3): 8.78 (d, J=7.9 Hz, 1H), 8.71 (d, J=8.0 Hz, 1H), 8.16 (d, J=7.9 Hz, 1H), 7.82 (d, J=7.6 Hz, 1H), 7.75-7.57 (m, 5H), 7.51 (d, J=7.0 Hz, 2H), 7.35 (t, J=7.1 Hz, 1H), 7.28 (t, J=7.4 Hz, 2H), 3.32 (dd, J=15.3, 5.9 Hz, 1H), 3.08 (dd, J=15.3, 6.7 Hz, 1H), 1.41-1.25 (m, 1H), 0.79-0.67 (m, 2H), 0.25 (s, 3H), 0.21 (s, 3H), 0.08-0.11 (m, 1H); .sup.13C NMR (150 MHz, CDCl.sub.3): 139.2, 136.0, 133.9, 132.1, 131.6, 130.7, 129.8, 128.9, 128.3, 127.8, 126.7, 126.6, 126.2, 126.1, 125.9, 124.5, 123.3, 122.5, 38.7, 15.5, 9.7, 4.2, 3.5, 3.7; .sup.29Si NMR (120 MHz, CDCl.sub.3): 2.8; HRMS (EI): Calculated for C.sub.26H.sub.26Si [M].sup.+: 366.1804, Found: 366.1803.

Inventive Example 26 Preparation of anti-{[(5-Bromo-1,3-phenylene)bis(methylene)]bis(cyclopropane-2,1-diyl)bis(dimethylphenylsilane)} (Anti-51)

(220) ##STR00103##

(221) Anti-{[(5-Bromo-1,3-phenylene)bis(methylene)]bis(cyclopropane-2,1-diyl)bis(dimethylphenylsilane)} (anti-51) (yield of 75%, dr.>99/1) was obtained via a reaction at 23 C. for 12 hours using the same method as Inventive Example 10 by adding 2,2-(5-bromo-1,3-phenylene)difuran (1s) instead of 2-methylfuran at 78 C. using 10.0 mol % B(C.sub.6F.sub.5).sub.3 and dimethylphenylsilane (8.0 eq.).

(222) Colorless liquid; .sup.1H NMR (600 MHz, CDCl.sub.3): 7.48 (d, J=6.2 Hz, 4H), 7.39-7.29 (m, 6H), 7.24 (s, 2H), 6.97 (s, 1H), 2.61 (dd, J=14.7, 6.5 Hz, 2H), 2.48 (dd, J=14.7, 6.8 Hz, 2H), 0.92 (q, J=6.7 Hz, 2H), 0.59-0.51 (m, 4H), 0.17 (s, 12H), 0.26 (q, J=7.8 Hz, 2H); .sup.13C NMR (150 MHz, CDCl.sub.3): 144.1, 138.9, 133.7, 128.86, 128.84, 127.6, 127.2, 122.1, 41.1, 16.6, 16.6, 9.16, 9.15, 3.7, 3.6, 3.8; .sup.29Si NMR (120 MHz, CDCl.sub.3): 2.9; HRMS (EI): Calculated for C.sub.30H.sub.37BrSi.sub.2 [M].sup.+: 532.1617, Found: 532.1616.

Inventive Example 27 Preparation of anti-1,3,5-Tris{[2-(dimethylphenylsilyl)cyclopropyl]methyl}benzene (Anti-52)

(223) ##STR00104##

(224) Anti-1,3,5-Tris{[2-(dimethylphenylsilyl)cyclopropyl]methyl}benzene (anti-52) (yield of 86%, dr.>99/1) was obtained via a reaction at 23 C. for 8 hours using the same method as Inventive Example 10 by adding 1,3,5-tri(furan-2-yl)benzene (1t) instead of 2-methylfuran at 78 C. using 20.0 mol % B(C.sub.6F.sub.5).sub.3 and dimethylphenylsilane (12.0 eq.).

(225) Colorless liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): 7.69-7.61 (m, 6H), 7.50-7.42 (m, 9H), 7.11 (s, 3H), 2.82-2.61 (m, 6H), 1.21-1.00 (m, 3H), 0.82-0.56 (m, 6H), 0.32 (s, 9H), 0.31 (s, 9H), 0.00-0.23 (m, 3H); .sup.13C NMR (150 MHz, CDCl.sub.3): 141.8, 139.3, 133.8, 128.9, 127.7, 126.2, 41.6, 17.0 (t, J=4.5 Hz, 3C), 9.2 (t, J=3.0 Hz, 3C), 3.6, 3.4, 3.6; .sup.29Si NMR (120 MHz, CDCl.sub.3): 2.8; HRMS (PSI): Calculated for C.sub.42H.sub.54NaSi.sub.3 [M+Na].sup.+: 665.3431, Found: 665.3432.

Inventive Example 28 Preparation of ((1S,2S)-2-(2-([1,1-biphenyl]-4-yl)ethyl)cyclopropyl)dimethyl(phenyl)silane (Anti-40)

(226) ##STR00105##

(227) ((1S,2S)-2-(2-([1,1-biphenyl]-4-yl)ethyl)cyclopropyl)dimethyl(phenyl)silane (anti-40) (yield of 71%, dr.>99/1) was obtained via a reaction for 10 hours using the same method as Inventive Example 10 except that 2-([1,1-biphenyl]-4-ylmethyl)furan (1ac) was used instead of 2-methylfuran.

(228) .sup.1H NMR (600 MHz, CDCl.sub.3): 7.71 (t, J=7.0 Hz, 4H), 7.63 (d, J=8.0 Hz, 2H), 7.54 (t, J=7.6 Hz, 2H), 7.50-7.46 (m, 3H), 7.44 (t, J=6.9 Hz, 1H), 7.35 (d, J=7.9 Hz, 2H), 2.92-2.81 (m, 2H), 1.93-1.84 (m, 1H), 1.73-1.62 (m, 1H), 0.94-0.82 (m, 1H), 0.67-0.52 (m, 2H), 0.35 (s, 3H), 0.33 (s, 3H), 0.19-0.28 (m, 1H); .sup.13C NMR (150 MHz, CDCl.sub.3): 141.8, 141.3, 139.4, 138.7, 133.9, 128.9, 128.9, 128.8, 127.8, 127.1, 38.0, 35.9, 15.9, 9.3, 3.9, 3.5, 3.6; .sup.29Si NMR (120 MHz, CDCl.sub.3): 2.9; HRMS (ESI): Calculated for C.sub.25H.sub.23NaSi [M+Na].sup.+: 379.1858, Found: 379.1852.

III. Preparation of Anti-Cyclopropyl Silane Derivative from -silyloxy-(Z)-alkenyl Silane Compound

Inventive Example 29 Preparation of anti-(2-Ethylcyclopropyl)dimethylphenylsilane (Anti-33)

(229) ##STR00106##

(230) B(C.sub.6F.sub.5).sub.3 (154 mg, 3.0 mol %) was dissolved in CH.sub.2Cl.sub.2 (0.2 mL), Z-2 (3.54 g, 10 mmol) and dimethylphenylsilane (2.0 g, 15 mmol) were sequentially added thereto at 0 C. and, then, the reaction mixture was stirred under argon gas at 23 C. for 12 hours. A conversion yield of 83% was verified via .sup.1H NMR analysis. After the reaction mixture was completely stirred, the reaction mixture was subjected to vacuum evaporation and was purified via silica gel flash column chromatography (eluant: hexane or mixture of hexane and ethyl acetate) to obtain anti-(2-Ethylcyclopropyl)dimethylphenylsilane (anti-33) as a colorless liquid (1.57 g, yield of 77%, dr.>99/1).

Inventive Example 30 Preparation of anti-(2-Ethylcyclopropyl)dimethylphenylsilane-d (Anti-35-d)

(231) ##STR00107##

(232) Anti-(2-Ethylcyclopropyl)dimethylphenylsilane-d (anti-35-d) (yield of 66%, dr.>99/1) was obtained via a reaction for 14 hours using the same method as Inventive Example 29 except that CD.sub.2Cl.sub.2 was used instead of CH.sub.2Cl.sub.2, PhMe.sub.2SiD was used instead of dimethylphenylsilane, and B(C.sub.6F.sub.5).sub.3 was used in 5.0 mol %.

(233) Colorless liquid; .sup.1H NMR (600 MHz, CD.sub.2Cl.sub.2): 7.66-7.59 (m, 2H), 7.43-7.35 (m, 3H), 1.45-1.40 (m, 0.6H), 1.30-1.21 (m, 0.4H), 1.02 (d, J=7.5 Hz, 3H), 0.75-0.67 (m, 1H), 0.51-0.42 (m, 2H), 0.26 (s, 3H), 0.24 (s, 3H), 0.33-0.46 (m, 1H); .sup.13C NMR (150 MHz, CD.sub.2Cl.sub.2): 140.1, 134.3, 129.2, 128.1, 29.0 (t=19.6 Hz), 18.1, 14.1, 9.2, 3.6, 3.4, 3.7; .sup.29Si NMR (120 MHz, CD.sub.2Cl.sub.2): 3.1; .sup.2H NMR (60 MHz, CD.sub.2Cl.sub.2): 1.58-1.36 (s, 0.4D), 1.36-1.12 (s, 0.6D); HRMS (ESI): Calculated for C.sub.13H.sub.20DSi [M+H].sup.+: 206.1475, Found: 206.1428.

Inventive Example 31 Preparation of 2-{2-[(1,1-Biphenyl)-4-yl]ethyl}cyclopropyl methanesulfonate (Anti-63)

(234) ##STR00108##

Preparation of anti-2-{2-[(1,1-Biphenyl)-4-yl]ethyl}cyclopropanol (Anti-62)

(235) B(C.sub.6F.sub.5).sub.3 (52 mg, 5.0 mol %) was dissolved in CH.sub.2Cl.sub.2 (1.0 mL), Ph.sub.2SiH.sub.2 (2.21 g, 12.0 mmol) was added thereto and, then, the resultant was stirred. 2-[(1,1-biphenyl)-4-ylmethyl]furan (1ac, 234 mg, 4.0 mmol) was added thereto at 0 C. and the reaction mixture was stirred at 23 C. for 10 hours. Et.sub.3N (5 eq based on B(C.sub.6F.sub.5).sub.3) was added to complete the reaction and, then, was subjected to vacuum evaporation. The evaporated remaining material was immediately used in Tamao oxidation. The evaporated remaining material was dissolved in THF/MeOH (20/20 mL), KF (2.32 g, 40 mmol), KHCO.sub.3 (4.04 g, 40 mmol), and 30% of hydrogen peroxide aqueous solution (130 mmol, 16 mL) were added and, then, the resultant was stirred at 23 C. for 16 hours.

(236) 10% of NaHSO.sub.3 aqueous solution (20 mL) was added to the reaction mixture at 0 C. to extract a water layer with diethyl ether (20 mL3). The obtained organic layer was washed with a saturated Na.sub.2CO.sub.3 aqueous solution (20 mL2), was dried with anhydrous MgSO.sub.4, was filtered, and was subjected to vacuum evaporation and, then, the remaining material was purified (to hexane/ethyl acetate 1/1) via silica gel column chromatography (hexane/ethyl acetate 1/1) to obtain anti-2-{2-[(1,1-Biphenyl)-4-yl]ethyl}cyclopropanol (anti-62) (621 g, 65% for two steps, dr.>99/1).

(237) Colorless solid; m.p. 91-92 C.; .sup.1H NMR (600 MHz, CDCl.sub.3): 7.67-7.59 (m, 2H), 7.58-7.53 (m, 2H), 7.46 (t, J=7.7 Hz, 2H), 7.41-7.34 (m, 1H), 7.29 (d, J=7.9 Hz, 2H), 3.21 (dt, J=6.2, 2.6 Hz, 1H), 2.88-2.67 (m, 2H), 2.15 (s, 1H), 1.67-1.56 (m, 1H), 1.54-1.45 (m, 1H), 1.10-0.94 (m, 1H), 0.83-0.63 (m, 1H), 0.38 (q, J=6.0 Hz, 1H); .sup.13C NMR (150 MHz, CDCl.sub.3): 141.4, 141.2, 138.8, 128.9, 128.81, 127.11 (2C), 127.07, 52.9, 35.0, 33.6, 20.7, 14.5; HRMS (ESI): Calculated for C.sub.17H.sub.17ONa [M+Na].sup.+: 260.1177, Found 260.1179.

Preparation of 2-{2-[(1,1-Biphenyl)-4-yl]ethyl}cyclopropyl methanesulfonate (Anti-63)

(238) Triethylamine (Et.sub.3N) (152 mg, 1.5 mmol), 4-dimethylaminopyridine (DMAP) (0.6 mg, 1 mol %), anti-62 (119 mg, 0.5 mmol), mesyl chloride (69 mg, 0.6 mmol), and CH.sub.2Cl.sub.2 (1.0 mL) were mixed at 0 C. and, then, were stirred at 23 C. for 6 hours. Water (3 mL) was added to complete a reaction and the reaction mixture was subjected to extraction with CH.sub.2Cl.sub.2 (3 mL3). An organic layer was dried with Na.sub.2SO.sub.4, was filtered, and was subjected to vacuum evaporation and, then, the remaining material was purified via silica gel column chromatography (hexane/ethyl acetate 7/3) to obtain 2-{2-[(1,1-Biphenyl)-4-yl]ethyl}cyclopropyl methanesulfonate (anti-63) (137 mg, 87%, dr.>99/1).

(239) Brown solid; m.p. 63-65 C.; .sup.1H NMR (600 MHz, CDCl.sub.3): 7.59 (d, J=7.8 Hz, 2H), 7.53 (d, J=8.2 Hz, 2H), 7.44 (t, J=7.7 Hz, 2H), 7.36-7.31 (m, 1H), 7.27 (d, J=7.8 Hz, 2H), 4.08-3.72 (m, 1H), 2.98 (s, 3H), 2.79 (t, J=7.6 Hz, 2H), 1.71-1.53 (m, 2H), 1.42-1.31 (m, 1H), 1.16-1.06 (m, 1H), 0.66 (q, J=6.7 Hz, 1H); .sup.13C NMR (150 MHz, CDCl.sub.3): 140.9, 140.4, 138.9, 128.8, 128.7, 127.1, 127.1, 126.9, 58.7, 37.6, 34.3, 32.7, 18.1, 12.1; HRMS (ESI): Calculated for C.sub.18H.sub.20NaO.sub.3S [M+Na].sup.+: 339.1031, Found: 339.1024.