METHOD OF PREPARING SILYLATIVE-REDUCED N-HETEROCYCLIC COMPOUND USING ORGANOBORON CATALYST

Abstract

Provided is a method of preparing a silylative-reduced N-heterocyclic compound by reducing an N-heteroaromatic compound including a sp.sup.2 hybridized nitrogen atom while simultaneously introducing a silyl group into a beta-position with respect to a nitrogen atom of the N-heteroaromatic compound, using a silane compound, in the presence of an organoboron catalyst.

Claims

1. A method of preparing a silylative-reduced N-heterocyclic compound by reducing an N-heteroaromatic compound including a central ring having 5 to 20 carbon atoms and a sp.sup.2 hybridized nitrogen atom while simultaneously introducing a silyl group into a beta-position with respect to a nitrogen atom of the N-heteroaromatic compound, using a silane compound, in the presence of an organoboron catalyst.

2. The method of claim 1, wherein an N-heterocyclic compound represented by the following Chemical Formula 1-1 is prepared by reacting a quinoline compound represented by the following Chemical Formula 2-1 with a silane compound represented by the following Chemical Formula 3-1, in the presence of the organoboron catalyst: ##STR00067## in Chemical Formulas 1-1, 2-1, and 3-1, R.sub.1 to R.sub.7 are each independently hydrogen, (C1-C10)alkyl, (C1-C10)alkoxy, (C6-C12)aryl, halogen or (C6-C12)aryloxy, or the R.sub.4 to R.sub.7 may be each independently linked to an adjacent substituent via (C3-C12)alkenylene with or without a fused ring to form a monocyclic or polycyclic aromatic ring, and the alkyl, aryl and aryloxy of R.sub.1 to R.sub.7 may be further substituted with (C1-C10)alkyl; R.sub.8 and R.sub.9 are each independently (C1-C10)alkyl or (C6-C12)aryl; and R.sub.10 is hydrogen or (C6-C12)aryl; provided that R.sub.8, R.sub.9 and R.sub.10 are not (C6-C12)aryl at the same time.

3. The method of claim 1, wherein an N-heterocyclic compound represented by the following Chemical Formula 1-2 is prepared by reacting an isoquinoline compound represented by the following Chemical Formula 2-2 with a silane compound represented by the following Chemical Formula 3-1, in the presence of the organoboron catalyst: ##STR00068## in Chemical Formulas 1-2, 2-2, and 3-1, R.sub.1 to R.sub.7 are each independently hydrogen, (C1-C10)alkyl, (C1-C10)alkoxy, (C6-C12)aryl, halogen or (C6-C12)aryloxy, or the R.sub.4 to R.sub.7 may be each independently linked to an adjacent substituent via (C3-C12)alkenylene with or without a fused ring to form a monocyclic or polycyclic aromatic ring, and the alkyl, aryl and aryloxy of R.sub.1 to R.sub.7 may be further substituted with (C1-C10)alkyl; R.sub.8 and R.sub.9 are each independently (C1-C10)alkyl or (C6-C12)aryl; and R.sub.10 is hydrogen or (C6-C12)aryl; provided that R.sub.8, R.sub.9 and R.sub.10 are not (C6-C12)aryl at the same time.

4. The method of claim 1, wherein an N-heterocyclic compound represented by the following Chemical Formula 1-3 is prepared by reacting a pyridine compound represented by the following Chemical Formula 2-3 with a silane compound represented by the following Chemical Formula 3-1, in the presence of the organoboron catalyst: ##STR00069## in Chemical Formulas 1-3, 2-3, and 3-1, R.sub.11 to R.sub.15 are each independently hydrogen, (C1-C10)alkyl, (C1-C10)alkoxy, (C6-C12)aryl, halogen or (C6-C12)aryloxy, and the alkyl, aryl and aryloxy of R.sub.11 to R.sub.15 may be further substituted with (C1-C10)alkyl; R.sub.8 and R.sub.9 are each independently (C1-C10)alkyl or (C6-C12)aryl; and R.sub.10 is hydrogen or (C6-C12)aryl; provided that R.sub.8, R.sub.9 and R.sub.10 are not (C6-C12)aryl at the same time.

5. The method of claim 1, wherein the organoboron catalyst is B(C.sub.6F.sub.5).sub.3 or B(C.sub.6F.sub.5).sub.2Ar, and the Ar is (C6-C12)aryl.

6. The method of claim 1, wherein the organoboron catalyst is used at 0.1 to 5.0 mol % based on 1 mol of the N-heteroaromatic compound.

7. The method of claim 6, wherein the organoboron catalyst is used at 1.0 to 5.0 mol % based on 1 mol of the N-heteroaromatic compound.

8. The method of claim 1, wherein the silane compound is used in amounts of 4 to 8 mol based on 1 mol of the N-heteroaromatic compound.

9. The method of claim 1, wherein the silylative-reduction is performed at a reaction temperature of 23 to 100° C.

10. The method of claim 1, wherein the silylative-reduction is performed by using one or two or more solvents selected from the group consisting of chloroform, dichloromethane, toluene, chlorobenzene, benzene, hexane and dichloroethane.

Description

BEST MODE

[0115] Hereinafter, a configuration of the present invention will be described in detail with reference to examples. These examples are to help understanding of the present invention, and it will be obvious to those skilled in the art that the scope of the present invention is not construed to be limited to these examples.

Preparation Example: Preparation of Quinoline Derivative

[Preparation Example 11] Preparation of 8-isopropylquinoline

[0116] ##STR00015##

[0117] A boric acid (4.1 mmol, 1.0 eq) and glycerol (16 mmol, 4.0 eq) were added to a mixture of FeSO.sub.4.7H.sub.2O (0.49 mmol, 0.12 eq), 2-isopropyl aniline (4.1 mmol, 1.0 eq) and nitro-benzene (0.25 mL) at room temperature. The reaction mixture was cooled to 0° C., and a concentrated sulfuric acid (14 mmol, 3.3 eq) was slowly added thereto. Then, the reaction mixture was heated to 150° C., and stirred for 11 hours. After the stirring was completed, the reaction mixture was cooled to room temperature, and water (2 mL) and saturated NaHCO.sub.3 aqueous solution (4 mL) were added thereto to thereby complete the reaction. Then, the reaction mixture was extracted with diethylether (10 mL×3), the obtained organic layer was washed with brine (30 mL×2), dried with anhydrous MgSO.sub.4, followed by filtration and decompression concentration, and the residue was purified by silica gel column chromatography (EA/Hx=1/20) to obtain 8-isopropylquinoline (527 mg, 75%).

[0118] Colorless oil; .sup.1H NMR (600 MHz, CDCl.sub.3) δ 8.95 (dd, J=4.2, 1.8 Hz, 1H), 8.12 (dd, J=8.2, 1.7 Hz, 1H), 7.64 (ddd, J=12.0, 7.7, 1.4 Hz, 2H), 7.51 (dd, J=7.6, 7.6 Hz, 1H), 7.37 (dd, J=8.2, 4.1 Hz, 1H), 4.38 (sep, J=6.9 Hz, 1H), 1.41 (d, J=7.0 Hz, 6H); .sup.13C NMR (150 MHz, CDCl.sub.3) δ 149.1, 147.3, 146.1, 136.4, 128.3, 126.4, 125.5, 125.1, 120.7, 27.1, 23.5 (2C); IR (cm.sup.−1) 2959, 2867, 1596, 1496, 1467, 1364, 1324, 1250, 1177, 1133, 1108, 1046, 1016, 828, 791, 755, 687; HRMS (EI): Calculated for C.sub.12H.sub.13N [M].sup.+: 171.1048, Found: 171.1047.

[Preparation Example 2] Preparation of 5-phenylquinoline

[0119] ##STR00016##

[0120] 5-bromo-quinoline (2.0 mmol, 1.0 eq), phenyl boric acid (3.0 mmol, 1.5 eq), Pd(PPh.sub.3).sub.4 (0.10 mmol, 5.0 mol %), K.sub.2CO.sub.3 (4.0 mmol, 2.0 eq), dioxane (8.0 mL) and water (2.0 mL) were mixed and refluxed at 90° C. After 12 hours, the reaction mixture was cooled at room temperature, and saturated NaHCO.sub.3 aqueous solution (10 mL) was added thereto to thereby complete the reaction. Next, the reaction mixture was extracted with ethyl acetate (10 mL×3), the obtained organic layer was washed with brine (20 mL×2), dried with anhydrous MgSO.sub.4, followed by filtration and decompression concentration, and the residue was purified by silica gel column chromatography (EA/Hx=1/10) to obtain 5-phenylquinoline (386 mg, 99%).

[0121] Bright yellow solid; .sup.1H NMR (600 MHz, CDCl.sub.3) δ 8.93 (dd, J=4.1, 1.7 Hz, 1H), 8.29-8.23 (m, 1H), 8.19-8.09 (m, 1H), 7.76 (dd, J=8.5, 7.0 Hz, 1H), 7.53-7.49 (m, 3H), 7.48-7.44 (m, 3H), 7.35 (dd, J=8.6, 4.1 Hz, 1H); .sup.13C NMR (150 MHz, CDCl.sub.3) δ 150.2, 148.5, 140.5, 139.4, 134.3, 130.0 (2C), 129.0, 128.9, 128.4 (2C), 127.6, 127.2, 126.7, 121.0.

[Preparation Example 3] Preparation of 7-phenylquinoline

[0122] ##STR00017##

[0123] 7-bromo-quinoline (2.0 mmol, 1.0 eq), phenyl boric acid (3.0 mmol, 1.5 eq), Pd(PPh.sub.3).sub.4 (0.10 mmol, 5.0 mol %), K.sub.2CO.sub.3 (4.0 mmol, 2.0 eq), dioxane (8.0 mL) and water (2.0 mL) were mixed and refluxed at 90° C. After 14 hours, the reaction mixture was cooled at room temperature, and saturated NaHCO.sub.3 aqueous solution (10 mL) was added thereto to thereby complete the reaction. Next, the reaction mixture was extracted with ethyl acetate (10 mL×3), the obtained organic layer was washed with brine (20 mL×2), dried with anhydrous MgSO.sub.4, followed by filtration and decompression concentration, and the residue was purified by silica gel column chromatography (EA/Hx=1/10) to obtain 7-phenylquinoline (386 mg, 94%).

[0124] Bright yellow oil; .sup.1H NMR (600 MHz, CDCl.sub.3) δ 8.95 (dd, J=4.2, 1.7 Hz, 1H), 8.35 (s, 1H), 8.18 (d, J=8.3 Hz, 1H), 7.89 (d, J=8.5 Hz, 1H), 7.83 (dd, J=8.5, 1.8 Hz, 1H), 7.81-7.68 (m, 2H), 7.51 (dd, J=8.3, 7.1 Hz, 2H), 7.46-7.34 (m, 2H); .sup.13C NMR (150 MHz, CDCl.sub.3) δ 150.8, 148.5, 142.3, 140.3, 135.8, 129.0 (2C), 128.2, 127.9, 127.5 (2C), 127.4, 127.1, 126.3, 121.0; IR (cm.sup.−1) 3035, 1736, 1619, 1488, 1427, 942, 891, 836, 753, 693, 566, 477; HRMS (EI): Calculated for C.sub.15H.sub.11N [M].sup.+: 205.0891, Found: 205.0889.

[Preparation Example 4] Preparation of 6-(p-tolyloxy)quinoline

[0125] ##STR00018##

[0126] 6-hydroxyquinoline (1.2 mmol, 1.2 eq), picolinic acid (0.20 mmol, 20 mol %), CuI (0.10 mmol, 10 mol %), K.sub.3PO.sub.4 (2.0 mmol, 2.0 eq), 1-bromo-4-methylbenzene (1.0 mmol, 1.0 eq), and DMSO (dimethylsulfoxide, 2.0 mL) were mixed and refluxed at 110° C. After 24 hours, the reaction mixture was cooled at room temperature, and water (1 mL) was added thereto to thereby complete the reaction. Next, the reaction mixture was extracted with ethyl acetate (10 mL×2), the obtained organic layer was washed with saturated ammonium chloride aqueous solution (20 mL×2), dried with anhydrous MgSO.sub.4, followed by filtration and decompression concentration, and the residue was purified by silica gel column chromatography (EA/Hx=1/4) to obtain 6-(p-tolyloxy)quinoline (202 mg, 86%).

[0127] Colorless oil; .sup.1H NMR (600 MHz, CDCl.sub.3) δ 8.77 (dd, J=4.2, 1.7 Hz, 1H), 8.06 (d, J=9.1 Hz, 1H), 7.96-7.84 (m, 1H), 7.45 (dd, J=9.1, 2.7 Hz, 1H), 7.28 (dd, J=8.3, 4.2 Hz, 1H), 7.19-7.09 (m, 3H), 6.97 (d, J=8.4 Hz, 2H), 2.33 (s, 3H); .sup.13C NMR (150 MHz, CDCl.sub.3) δ 156.0, 153.8, 148.6, 144.8, 134.9, 133.6, 131.1, 130.3 (2C), 128.9, 122.8, 121.2, 119.6 (2C), 111.9, 20.6; IR (cm.sup.−1) 3023, 2954, 1595, 1494, 1462, 1374, 1322, 960, 825; HRMS (EI): Calculated for C.sub.16H.sub.13NO [M].sup.+: 235.0997, found: 235.0998.

Example I: Preparation of silvlative-reduced tetrahydroquinoline compound (Chemical Formula 1-1)

[Example 1] Preparation of 3-(diethylsilyl)-1,2,3,4-tetrahydroquinoline (1b)

[0128] ##STR00019##

[0129] B(C.sub.6F.sub.5).sub.3 (0.0050 mmol, 1.0 mol %) was dissolved in chloroform (0.50 mL) in a 2.5 mL reaction vial, then diethylsilane (2.0 mmol, 4.0 eq) and quinoline (1a, 0.50 mmol, 1.0 eq) were sequentially added thereto. The reaction mixture was stirred at 65° C. for 6 hours, cooled to room temperature, and filtrated by passing through a silica gel pad with dichloromethane (15 mL) and methanol (2 mL). After decompression concentration of the filtrate, the residue was purified by silica gel column chromatography (EA/Hx=5/95) to obtain 3-(diethylsilyl)-1,2,3,4-tetrahydroquinoline (1b) (yield: 86%).

[0130] Colorless oil; .sup.1H NMR (600 MHz, CDCl.sub.3) δ 7.11-6.87 (m, 2H), 6.61 (ddd, J=7.6, 1.3, 1.3 Hz, 1H), 6.47 (d, J=7.9 Hz, 1H), 3.89 (br, 1H), 3.63 (d, J=3.1 Hz, 1H), 3.39 (ddd, J=11.6, 3.4, 1.7 Hz, 1H), 3.23 (t, J=11.4 Hz, 1H), 2.87-2.64 (m, 2H), 1.46 (tdd, J=11.4, 5.7, 2.9 Hz, 1H), 1.04 (td, J=7.9, 1.4 Hz, 6H), 0.69 (tdd, J=11.3, 6.3, 3.3 Hz, 4H); .sup.13C NMR (150 MHz, CDCl.sub.3) δ 144.5, 129.0, 126.7, 121.8, 116.9, 114.3, 44.0, 29.1, 17.7, 8.3 (2C), 1.3, 1.2; .sup.29Si NMR (120 MHz, CDCl.sub.3) δ 0.15; IR (cm.sup.−1) 3403, 2951, 2828, 2093, 1604, 1502, 1262, 1246, 1008, 803, 742; HRMS (EI): Calculated for C.sub.13H.sub.21NSi [M].sup.+: 219.1443, Found: 219.1442.

[Example 2] Preparation of 3-(diethylsilyl)-6-methyl-1,2,3,4-tetrahydroquinoline (2b)

[0131] ##STR00020##

[0132] 3-(diethylsilyl)-6-methyl-1,2,3,4-tetrahydroquinoline (2b) (yield: 85%) was obtained by the same method as Example 1 above except for using 6-methylquinoline (2a) instead of quinoline (1a).

[0133] Bright yellow oil; .sup.1H NMR (600 MHz, CDCl.sub.3) δ 6.94-6.88 (m, 2H), 6.51 (d, J=8.0 Hz, 1H), 3.84-3.76 (m, 2H), 3.46 (ddd, J=11.5, 2.2, 2.2 Hz, 1H), 3.30 (t, J=11.4 Hz, 1H), 2.88-2.83 (m, 2H), 2.35 (s, 3H), 1.58 (dtd, J=10.9, 6.9, 3.2 Hz, 1H), 1.18 (td, J=7.9, 1.3 Hz, 6H), 0.82 (qt, J=8.0, 3.3 Hz, 4H); .sup.13C NMR (150 MHz, CDCl.sub.3) (142.1, 129.4, 127.1, 125.8, 121.7, 114.4, 44.1, 29.0, 20.3, 17.8, 8.3 (2C), 1.2, 1.1; .sup.29Si NMR (120 MHz, CDCl.sub.3) δ 0.43; IR (cm.sup.−1) 3391, 2951, 2872, 2093, 1618, 1510, 1266, 1249, 1232, 1009, 802; HRMS (EI): Calculated for C.sub.14H.sub.23NSi [M].sup.+: 233.1600, Found: 233.1601.

[Example 3] Preparation of 3-(diethylsilyl)-7-methyl-1,2,3,4-tetrahydroquinoline (3b)

[0134] ##STR00021##

[0135] 3-(diethylsilyl)-7-methyl-1,2,3,4-tetrahydroquinoline (3b) (yield: 81%) was obtained by the same method as Example 1 above except for using 7-methylquinoline (3a) instead of quinoline (1a).

[0136] Yellow oil; .sup.1H NMR (600 MHz, CDCl.sub.3) δ 6.86 (dd, J=7.9, 2.0 Hz, 1H), 6.47 (dd, J=7.7, 1.9 Hz, 1H), 6.33 (s, 1H), 3.60 (br, 1H), 3.71-3.58 (m, 1H), 3.45-3.29 (m, 1H), 3.28-3.14 (m, 1H), 2.84-2.67 (m, 2H), 2.25 (s, 3H), 1.47 (ddt, J=11.4, 5.6, 2.9 Hz, 1H), 1.06 (td, J=7.9, 2.4 Hz, 6H), 0.82-0.57 (m, 4H); .sup.13C NMR (150 MHz, CDCl.sub.3) δ 144.4, 136.3, 128.8, 118.9, 117.8, 114.8, 44.0, 28.7, 21.1, 17.9, 8.3 (2C), 1.4, 1.2; .sup.29Si NMR (120 MHz, CDCl.sub.3) δ 0.37; IR (cm.sup.−1): 3417, 2952, 2873, 2097, 1600, 1501, 1258, 1228, 806, 752; HRMS (EI): Calculated for C.sub.14H.sub.23NSi [M].sup.+: 233.1600, Found: 233.1601.

[Example 4] Preparation of 3-(diethylsilyl)-8-methyl-1,2,3,4-tetrahydroquinoline (4b)

[0137] ##STR00022##

[0138] 3-(diethylsilyl)-8-methyl-1,2,3,4-tetrahydroquinoline (4b) (yield: 96%) was obtained by the same method as Example 1 above except for using 8-methylquinoline (4a) instead of quinoline (1a).

[0139] Bright yellow oil; .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.10-6.80 (m, 2H), 6.68 (dd, J=7.4, 7.4 Hz, 1H), 3.77 (q, J=3.1 Hz, 1H), 3.73 (br, 1H) 3.69-3.51 (m, 1H), 3.38 (t, J=11.5 Hz, 1H), 3.06-2.67 (m, 2H), 2.19 (s, 3H), 1.76-1.38 (m, 1H), 1.16 (t, J=7.9 Hz, 6H), 0.90-0.68 (m, 4H); .sup.13C NMR (100 MHz, CDCl.sub.3) δ 142.4, 127.7, 126.8, 121.20, 121.19, 116.2, 44.3, 29.4, 17.8, 17.0, 8.35, 8.33, 1.3, 1.1; .sup.29Si NMR (120 MHz, CDCl.sub.3) δ 0.43; IR (cm.sup.−1): 3422, 2951, 2872, 2092, 1598, 1492, 1264, 1247, 1223, 1008, 803, 753; HRMS (EI): Calculated for C.sub.14H.sub.23NSi [M].sup.+: 233.1600, Found: 233.1599.

[Example 5] Preparation of 3-(diethylsilyl)-8-isopropyl-1,2,3,4-tetrahydroquinoline (5b)

[0140] ##STR00023##

[0141] 3-(diethylsilyl)-8-isopropyl-1,2,3,4-tetrahydroquinoline (5b) (yield: 90%) was obtained by the same method as Example 1 above except for using 8-isopropylquinoline (5a) instead of quinoline (1a).

[0142] Colorless oil; .sup.1H NMR (600 MHz, CDCl.sub.3) δ 7.07-6.97 (m, 1H), 6.86 (dd, J=7.5, 1.4 Hz, 1H), 6.66 (d, J=7.5, 7.5 Hz, 1H), 3.93 (s, 1H), 3.67 (q, J=3.1 Hz, 1H), 3.56-3.50 (m, 1H), 3.30 (t, J=11.5 Hz, 1H), 2.95-2.75 (m, 3H), 1.56-1.43 (m, 1H), 1.27 (d, J=6.8 Hz, 6H), 1.06 (t, J=7.9 Hz, 6H), 0.77-0.64 (m, 4H); .sup.13C NMR (150 MHz, CDCl.sub.3) δ 141.2, 131.6, 126.8, 122.7, 121.7, 116.6, 44.5, 29.9, 26.9, 22.5, 22.2, 17.6, 8.40, 8.37, 1.4, 1.2; .sup.29Si NMR (120 MHz, CDCl.sub.3) δ 0.39; IR (cm.sup.−1) 2954, 2873, 2093, 1596, 1491, 1459, 1349, 1261, 1010, 967, 804, 740; HRMS (EI): Calculated for C.sub.16H.sub.27NSi [M].sup.+: 261.1913, Found: 261.1909.

[Example 6] Preparation of 3-(diethylsilyl)-5-phenyl-1,2,3,4-tetrahydroquinoline (6b)

[0143] ##STR00024##

[0144] 3-(diethylsilyl)-5-phenyl-1,2,3,4-tetrahydroquinoline (6b) (yield: 70%) was obtained by the same method as Example 1 above except for using 5-phenylquinoline (6a) instead of quinoline (1a).

[0145] Colorless oil; .sup.1H NMR (600 MHz, CDCl.sub.3) δ 7.38 (dd, J=8.6, 6.7 Hz, 2H), 7.35-7.28 (m, 3H), 7.01 (t, J=7.7 Hz, 1H), 6.60-6.53 (m, 1H), 6.48 (dd, J=8.2, 1.3 Hz, 1H), 3.58-3.47 (m, 1H), 3.43-3.35 (m, 1H), 3.24 (t, J=11.3 Hz, 1H), 2.69-2.61 (m, 1H), 2.55 (dd, J=16.5, 11.7 Hz, 1H), 1.31 (d, J=3.6 Hz, 1H), 0.94 (dtd, J=14.5, 7.9, 1.2 Hz, 6H), 0.70-0.40 (m, 4H); .sup.13C NMR (150 MHz, CDCl.sub.3) δ 144.6, 142.2, 141.8, 129.1 (2C), 127.8 (2C), 126.5, 126.3, 119.3, 118.7, 113.5, 43.9, 27.7, 17.7, 8.31, 8.29, 1.3, 1.2; .sup.29Si NMR (120 MHz, CDCl.sub.3) δ 0.39; IR (cm.sup.−1): 3405, 2952, 2873, 2096, 1588, 1487, 1459, 1257, 1011, 810, 759; HRMS (EI): Calculated C.sub.19H.sub.25NSi [M].sup.+: 295.1756, Found: 295.1754.

[Example 7] Preparation of 3-(diethylsilyl)-7-phenyl-1,2,3,4-tetrahydroquinoline (7b)

[0146] ##STR00025##

[0147] 3-(diethylsilyl)-7-phenyl-1,2,3,4-tetrahydroquinoline (7b) (yield: 61%) was obtained by the same method as Example 1 above except for using 7-phenylquinoline (7a) instead of quinoline (1a).

[0148] White solid; m.p. 55-57° C.; .sup.1H NMR (600 MHz, CDCl.sub.3) δ 7.56 (dt, J=7.8, 1.7 Hz, 2H), 7.41 (td, J=7.7, 2.2 Hz, 2H), 7.32 (tt, J=7.7, 1.4 Hz, 1H), 7.02 (dd, J=7.7, 2.3 Hz, 1H), 6.86 (dt, J=7.7, 2.1 Hz, 1H), 6.71 (t, J=2.0 Hz, 1H), 3.71-3.63 (m, 1H), 3.51-3.38 (m, 1H), 3.28 (td, J=11.4, 2.3 Hz, 1H), 2.90-2.71 (m, 2H), 1.51 (dtd, J=8.9, 5.9, 3.0 Hz, 1H), 1.14-1.00 (m, 6H), 0.72 (dq, J=8.4, 2.7 Hz, 4H); .sup.13C NMR (150 MHz, CDCl.sub.3) δ 144.8, 141.6, 140.0, 129.4, 128.5 (2C), 126.9 (2C), 126.8, 121.2, 116.0, 112.9, 44.1, 28.9, 17.8, 8.4 (2C), 1.4, 1.2; .sup.29Si NMR (120 MHz, CDCl.sub.3) δ 0.39; IR (cm.sup.−1) 2951, 2908, 2872, 2090, 1609, 1565, 1484, 1386, 1319, 1288, 1260, 1226, 1008, 804, 757, 695; HRMS (EI): Calculated for C.sub.19H.sub.25NSi [M].sup.+: 295.1756, Found: 295.1754.

[Example 8] Preparation of 3-(diethylsilyl)-4-methyl-1,2,3,4-tetrahydroquinoline (8b)

[0149] ##STR00026##

[0150] 3-(diethylsilyl)-4-methyl-1,2,3,4-tetrahydroquinoline (8b) (yield: 95%) was obtained by the same method as Example 1 above except for using 4-methylquinoline (8a) instead of quinoline (1a) and stirring for 24 hours.

[0151] Yellow oil; .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.13-7.06 (m, 1H), 7.00 (dddd, J=7.9, 7.2, 1.5, 0.6 Hz, 1H), 6.69 (td, J=7.4, 1.3 Hz, 1H), 6.51 (dd, J=8.0, 1.3 Hz, 1H), 3.63 (td, J=3.4, 2.7 Hz, 1H), 3.52 (dd, J=11.3, 3.6 Hz, 1H), 3.25 (ddd, J=11.3, 6.0, 0.7 Hz, 1H), 2.96 (dd, J=7.0, 4.7 Hz, 1H), 1.39 (d, J=7.0 Hz, 3H), 1.28-1.18 (m, 1H), 1.08-0.91 (m, 6H), 0.72-0.52 (m, 4H); .sup.13C NMR (100 MHz, CDCl.sub.3) δ 144.6, 128.9, 126.8, 126.5, 117.2, 114.4, 40.5, 32.1, 25.2, 25.1, 8.5, 8.4, 1.9, 1.7; .sup.29Si NMR (120 MHz, CDCl.sub.3) δ 0.49; IR (cm.sup.−1): 3392, 2953, 2872, 2092, 1783, 1606, 1499, 1260, 1228, 1014, 814, 744; HRMS (EI): Calculated for C.sub.14H.sub.23NSi [M].sup.+: 233.1600, Found: 233.1603.

[Example 9] Preparation of 3-(diethylsilyl)-3-methyl-1,2,3,4-tetrahydroquinoline (9b)

[0152] ##STR00027##

[0153] 3-(diethylsilyl)-3-methyl-1,2,3,4-tetrahydroquinoline (9b) (yield: 92%) was obtained by the same method as Example 1 above except for using 3-methylquinoline (9a) instead of quinoline (1a) and stirring for 24 hours.

[0154] Colorless oil; .sup.1H NMR (600 MHz, CDCl.sub.3) δ 7.00 (ddd, J=7.8, 7.0, 1.5 Hz, 1H), 6.96 (dt, J=7.5, 1.2 Hz, 1H), 6.64 (td, J=7.4, 1.2 Hz, 1H), 6.49 (dd, J=8.0, 1.2 Hz, 1H), 3.85 (br, 1H), 3.61-3.47 (m, 1H), 3.32 (dd, J=11.2, 1.1 Hz, 1H), 2.99 (dd, J=11.3, 1.6 Hz, 1H), 2.91 (d, J=16.1 Hz, 1H), 2.48 (d, J=16.1 Hz, 1H), 1.30-0.91 (m, 9H), 0.81-0.45 (m, 4H); .sup.13C NMR (150 MHz, CDCl.sub.3) δ 144.1, 129.7, 126.5, 120.0, 116.9, 113.7, 49.9, 36.9, 20.9, 19.3, 8.9, 8.8, 0.8, 0.6; .sup.29Si NMR (120 MHz, CDCl.sub.3) δ 6.71; IR (cm.sup.−1) 3397, 2951, 2828, 2092, 1617, 1487, 1261, 1232, 1010, 787; HRMS (EI): Calculated for C.sub.14H.sub.23NSi [M].sup.+: 233.1600, Found: 233.1598.

[Example 10] Preparation of 5-chloro-3-(diethylsilyl)-1,2,3,4-tetrahydroquinoline (10b)

[0155] ##STR00028##

[0156] 5-chloro-3-(diethylsilyl)-1,2,3,4-tetrahydroquinoline (10b) (yield: 94%) was obtained by the same method as Example 1 above except for using 5-chloroquinoline (10a) instead of quinoline (1a).

[0157] Yellow oil; .sup.1H NMR (600 MHz, CDCl.sub.3) δ 6.91 (t, J=7.9 Hz, 1H), 6.72 (dd, J=8.0, 1.3 Hz, 1H), 6.38 (d, J=8.0 Hz, 1H), 4.01 (s, 1H), 3.82-3.56 (m, 1H), 3.37 (ddd, J=11.5, 3.4, 1.9 Hz, 1H), 3.19 (t, J=11.4 Hz, 1H), 3.03 (ddd, J=17.1, 5.1, 1.9 Hz, 1H), 2.61 (dd, J=17.0, 12.0 Hz, 1H), 1.45 (dt, J=5.8, 3.4 Hz, 1H), 1.10 (tdt, J=8.0, 2.6, 1.3 Hz, 6H), 0.83-0.51 (m, 4H); .sup.13C NMR (150 MHz, CDCl.sub.3) δ 146.1, 134.3, 126.9, 119.3, 117.3, 112.5, 43.3, 26.6, 17.3, 8.3 (2C), 1.3, 1.1; .sup.29Si NMR (120 MHz, CDCl.sub.3) δ 0.52; IR (cm.sup.−1): 3413, 2952, 2873, 2095, 1596, 1487, 1260, 1233, 1009, 807, 762; HRMS (EI): Calculated for C.sub.13H.sub.20ClNSi [M].sup.+: 253.1054, Found: 253.1051.

[Example 11] Preparation of 5-bromo-3-(diethylsilyl)-1,2,3,4-tetrahydroquinoline (11 b)

[0158] ##STR00029##

[0159] 5-bromo-3-(diethylsilyl)-1,2,3,4-tetrahydroquinoline (11b) (yield: 85%) was obtained by the same method as Example 1 above except for using 5-bromoquinoline (11a) instead of quinoline (1a).

[0160] Colorless oil; .sup.1H NMR (600 MHz, CDCl.sub.3) δ 6.87 (dd, J=7.8, 1.2 Hz, 1H), 6.82 (t, J=7.9 Hz, 1H), 6.41 (dd, J=8.0, 1.2 Hz, 1H), 4.01 (s, 1H), 3.68 (q, J=3.1 Hz, 1H), 3.35 (ddd, J=11.5, 3.5, 1.9 Hz, 1H), 3.17 (t, J=11.4 Hz, 1H), 2.96 (ddd, J=17.0, 5.0, 1.9 Hz, 1H), 2.69-2.49 (m, 1H), 1.50-1.35 (m, 1H), 1.06 (td, J=7.9, 3.6 Hz, 6H), 0.72 (dddd, J=12.8, 8.0, 7.0, 3.3 Hz, 4H); .sup.13C NMR (150 MHz, CDCl.sub.3) δ 146.3, 127.5, 125.6, 121.0, 120.6, 113.3, 43.5, 29.7, 17.8, 8.4, 8.3, 1.4, 1.2; .sup.29Si NMR (120 MHz, CDCl.sub.3) δ 0.38; IR (cm.sup.−1) 2952, 2873, 2093, 1593, 1486, 1457, 1344, 1312, 1260, 1230, 1193, 805, 759; HRMS (EI): Calculated for C.sub.13H.sub.20BrNSi [M].sup.+: 297.0548, Found: 297.0551.

[Example 12] Preparation of 3-(diethylsilyl)-6-fluoro-1,2,3,4-tetrahydroquinoline (12b)

[0161] ##STR00030##

[0162] 3-(diethylsilyl)-6-fluoro-1,2,3,4-tetrahydroquinoline (12b) (yield: 73%) was obtained by the same method as Example 1 above except for using 6-fluoroquinoline (12a) instead of quinoline (1a).

[0163] Colorless oil; .sup.1H NMR (600 MHz, CDCl.sub.3) δ 6.75-6.64 (m, 2H), 6.40 (dd, J=8.4, 4.8 Hz, 1H), 3.65 (q, J=3.1 Hz, 1H), 3.37 (ddd, J=11.4, 3.4, 1.6 Hz, 1H), 3.19 (t, J=11.4 Hz, 1H), 2.81-2.63 (m, 2H), 1.47-1.34 (m, 1H), 1.05 (td, J=7.9, 1.4 Hz, 6H), 0.80-0.53 (m, 4H); .sup.13C NMR (150 MHz, CDCl.sub.3) δ 155.4 (d, J=234.9 Hz), 140.7 (d, J=1.8 Hz), 123.1 (d, J=6.3 Hz), 115.2 (d, J=21.4 Hz), 115.0 (d, J=7.5 Hz), 113.2 (d, J=22.5 Hz), 44.2, 29.2, 17.6, 8.3 (2C), 1.3, 1.2; .sup.19F NMR (564 MHz, CDCl.sub.3) δ −128.1 (td, J=8.8, 4.9 Hz); .sup.29Si NMR (120 MHz, CDCl.sub.3) 0.39; IR (cm.sup.−1) 2953, 2910, 2874, 2095, 1503, 1348, 1243, 1221, 1221, 1140, 850, 800; HRMS (EI): Calculated for C.sub.13H.sub.20FNSi [M].sup.+: 237.1349, Found: 237.1349.

[Example 13] Preparation of 6-bromo-3-(diethylsilyl)-1,2,3,4-tetrahydroquinoline (13b)

[0164] ##STR00031##

[0165] 6-bromo-3-(diethylsilyl)-1,2,3,4-tetrahydroquinoline (13b) (yield: 94%) was obtained by the same method as Example 1 above except for using 6-bromoquinoline (13a) instead of quinoline (1a).

[0166] Colorless oil; .sup.1H NMR (600 MHz, CDCl.sub.3) δ 7.04 (d, J=9.1 Hz, 2H), 6.33 (dd, J=8.1, 1.6 Hz, 1H), 3.87 (br, 1H), 3.65 (q, J=3.2, 2.8 Hz, 1H), 3.49-3.28 (m, 1H), 3.20 (td, J=11.4, 1.6 Hz, 1H), 2.72 (qd, J=16.3, 8.1 Hz, 2H), 1.40 (td, J=4.7, 2.2 Hz, 1H), 1.05 (tt, J=7.9, 1.2 Hz, 6H), 0.70 (dt, J=7.7, 2.6 Hz, 4H); .sup.13C NMR (150 MHz, CDCl.sub.3) δ 143.4, 131.3, 129.2, 123.7, 115.5, 108.0, 43.8, 29.0, 17.2, 8.3 (2C), 1.3, 1.1; .sup.29Si NMR (120 MHz, CDCl.sub.3) δ 0.32; IR (cm.sup.−1) 3411, 2950, 2872, 2089, 1598, 1491, 1261, 1243, 1229, 1004, 800, 705; HRMS (EI): Calculated for C.sub.13H.sub.20BrNSi [M].sup.+: 297.0548, Found: 297.0551.

[Example 14] Preparation of 7-chloro-3-(diethylsilyl)-1,2,3,4-tetrahydroquinoline (14b)

[0167] ##STR00032##

[0168] 7-chloro-3-(diethylsilyl)-1,2,3,4-tetrahydroquinoline (14b) (yield: 87%) was obtained by the same method as Example 1 above except for using 7-chloroquinoline (14a) instead of quinoline (1a) and stirring at 23° C. for 6 hours.

[0169] Bright yellow oil; .sup.1H NMR (600 MHz, CDCl.sub.3) δ 6.81 (d, J=8.0 Hz, 1H), 6.53 (dd, J=8.0, 2.1 Hz, 1H), 6.42 (d, J=2.1 Hz, 1H), 3.89 (br, 1H), 3.62 (q, J=3.1 Hz, 1H), 3.37 (ddd, J=11.7, 3.6, 2.0 Hz, 1H), 3.19 (t, J=11.4 Hz, 1H), 2.86-2.47 (m, 2H), 1.39 (dt, J=4.6, 3.3 Hz, 1H), 1.02 (td, J=7.9, 1.2 Hz, 6H), 0.67 (dd, J=7.7, 3.6 Hz, 4H); .sup.13C NMR (150 MHz, CDCl.sub.3) δ 145.4, 131.8, 129.9, 120.0, 116.4, 113.4, 43.7, 28.7, 17.3, 8.3 (2C), 1.3, 1.2; .sup.29Si NMR (120 MHz, CDCl.sub.3) δ 0.36; IR (cm.sup.−1): 3410, 2953, 2873, 2098, 1600, 1497, 1259, 1238, 1080, 882, 784; HRMS (EI): Calculated for C.sub.13H.sub.20ClNSi [M].sup.+: 253.1054, Found: 253.1053.

[Example 15] Preparation of 8-chloro-3-(diethylsilyl)-1,2,3,4-tetrahydroquinoline (15b)

[0170] ##STR00033##

[0171] 8-chloro-3-(diethylsilyl)-1,2,3,4-tetrahydroquinoline (15b) (yield: 94%) was obtained by the same method as Example 1 above except for using 8-chloroquinoline (15a) instead of quinoline (1a) and stirring at 23° C. for 6 hours.

[0172] Colorless oil; .sup.1H NMR (600 MHz, CDCl.sub.3) δ 7.11-6.93 (m, 1H), 6.89-6.68 (m, 1H), 6.51 (t, J=7.7 Hz, 1H), 4.49 (br, 1H), 3.64 (q, J=3.1 Hz, 1H), 3.51 (ddd, J=11.7, 3.6, 2.0 Hz, 1H), 3.28 (t, J=11.6 Hz, 1H), 3.04-2.56 (m, 2H), 1.47-1.36 (m, 1H), 1.09-0.93 (m, 6H), 0.74-0.64 (m, 4H); .sup.13C NMR (150 MHz, CDCl.sub.3) δ 140.5, 127.1, 126.7, 123.1, 118.1, 116.1, 43.8, 29.4, 17.2, 8.3, 1.3, 1.2; .sup.29Si NMR (80 MHz, CDCl.sub.3) δ 0.37; IR (cm.sup.−1): 3421, 2953, 2092, 1600, 1491, 1332, 1261, 1229, 1051, 801, 784; HRMS (EI): Calculated for C.sub.13H.sub.20ClNSi [M].sup.+: 253.1054, Found: 253.1053.

[Example 16] Preparation of 8-bromo-3-(diethylsilyl)-1,2,3,4-tetrahydroquinoline (16b)

[0173] ##STR00034##

[0174] 8-bromo-3-(diethylsilyl)-1,2,3,4-tetrahydroquinoline (16b) (yield: 91%) was obtained by the same method as Example 1 above except for using 8-bromoquinoline (16a) instead of quinoline (1a) and stirring at 23° C. for 10 mins.

[0175] Colorless oil; .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.27 (dt, J=7.8, 1.3 Hz, 1H), 6.92 (dt, J=7.4, 1.2 Hz, 1H), 6.49 (dd, J=8.4, 6.9 Hz, 1H), 4.56 (br, 1H), 3.68 (d, J=3.0 Hz, 1H), 3.60-3.47 (m, 1H), 3.32 (t, J=11.6 Hz, 1H), 2.91-2.59 (m, 2H), 1.45 (dd, J=3.1, 2.0 Hz, 1H), 1.08 (td, J=7.8, 1.1 Hz, 6H), 0.77-0.61 (m, 4H); .sup.13C NMR (100 MHz, CDCl.sub.3) δ 141.4, 129.9, 127.8, 123.3, 116.7, 108.7, 44.1, 29.6, 17.1, 8.3 (2C), 1.3, 1.1; .sup.29Si NMR (120 MHz, CDCl.sub.3) δ 0.27; IR (cm.sup.−1): 3413, 2951, 2872, 2094, 1598, 1498, 1284, 1258, 1232, 1064, 803, 749; HRMS (EI): Calculated for C.sub.13H.sub.20BrNSi [M].sup.+: 297.0548, Found: 297.0546.

[Example 17] Preparation of 8-bromo-3-(diethylsilyl)-2-methyl-1,2,3,4-tetrahydroquinoline (17b)

[0176] ##STR00035##

[0177] 8-bromo-3-(diethylsilyl)-2-methyl-1,2,3,4-tetrahydroquinoline (17b) (yield: 81%) was obtained by the same method as Example 1 above except for using 8-bromo-2-methylquinoline (17a) instead of quinoline (1a) and stirring at 23° C. for 6 hours.

[0178] Colorless oil; .sup.1H NMR (600 MHz, CDCl.sub.3) δ 7.38-7.07 (m, 1H), 6.89 (dt, J=7.5, 1.5 Hz, 1H), 6.44 (td, J=7.7, 1.2 Hz, 1H), 4.54 (s, 1H), 3.77 (dt, J=6.8, 3.4 Hz, 1H), 3.69 (ddd, J=5.3, 2.3, 1.2 Hz, 1H), 3.03-2.43 (m, 2H), 1.47 (ddt, J=8.6, 5.0, 1.9 Hz, 1H), 1.23 (dd, J=6.6, 1.5 Hz, 3H), 1.00 (dtt, J=18.5, 7.8, 1.3 Hz, 6H), 0.78-0.30 (m, 4H); .sup.13C NMR (150 MHz, CDCl.sub.3) δ 140.9, 130.0, 127.8, 122.63, 116.5, 108.9, 48.2, 26.5, 22.3, 20.4, 8.4, 8.38, 1.9, 1.7; .sup.29Si NMR (120 MHz, CDCl.sub.3) δ −1.14; IR (cm.sup.−1): 3423, 2951, 2872, 2094, 1600, 1459, 1284, 1260, 1232, 1009, 918, 752; HRMS (ESI): Calculated for C.sub.14H.sub.23BrNSi [M+H].sup.+: 314.0763, Found: 314.0737.

[Example 18] Preparation of 3-(diethylsilyl)-6-(p-tolyloxy)-1,2,3,4-tetrahydroquinoline (20b)

[0179] ##STR00036##

[0180] 3-(diethylsilyl)-6-(p-tolyloxy)-1,2,3,4-tetrahydroquinoline (20b) (yield: 88%) was obtained by the same method as Example 1 above except for using 6-(p-tolyloxy)quinoline (20a) instead of quinoline (1a) and stirring for 12 hours.

[0181] Bright yellow oil; .sup.1H NMR (600 MHz, CDCl.sub.3) δ 7.12-7.05 (m, 2H), 6.89-6.83 (m, 2H), 6.72-6.64 (m, 2H), 6.46 (d, J=8.5 Hz, 1H), 3.64 (q, J=3.1 Hz, 1H), 3.44-3.33 (m, 1H), 3.22 (t, J=11.4 Hz, 1H), 2.73 (d, J=8.5 Hz, 2H), 2.31 (s, 3H), 1.52-1.39 (m, 1H), 1.04 (t, J=7.9 Hz, 6H), 0.82-0.50 (m, 4H); .sup.13C NMR (150 MHz, CDCl.sub.3) (156.7, 147.8, 140.81, 131.2, 129.8 (2C), 123.1, 120.3, 118.4, 117.3 (2C), 115.2, 44.2, 29.2, 20.5, 17.7, 8.3 (2C), 1.3, 1.1; .sup.29Si NMR (120 MHz, CDCl.sub.3) δ 0.42; IR (cm.sup.−1): 3406, 2951, 2872, 2093, 1607, 1495, 1286, 1226, 1011, 805; HRMS (EI): Calculated for C.sub.20H.sub.27NOSi [M].sup.+: 325.1862, Found: 325.1863.

[Example 19] Preparation of 3-(diethylsilyl)-4,6,8-trimethyl-1,2,3,4-tetrahydroquinoline (21b)

[0182] ##STR00037##

[0183] 3-(diethylsilyl)-4,6,8-trimethyl-1,2,3,4-tetrahydroquinoline (21b) (yield: 80%) was obtained by the same method as Example 1 above except for using 4,6,8-trimethylquinoline (21a) instead of quinoline (1a).

[0184] Colorless oil; .sup.1H NMR (600 MHz, CDCl.sub.3) δ 6.87-6.81 (m, 1H), 6.81-6.73 (m, 1H), 3.65 (q, J=3.1 Hz, 1H), 3.56 (dd, J=11.3, 3.6 Hz, 1H), 3.31 (dd, J=11.3, 6.3 Hz, 1H), 3.02-2.88 (m, 1H), 2.27 (s, 3H), 2.11 (s, 3H), 1.41 (d, J=6.9 Hz, 3H), 1.24 (dtd, J=5.1, 2.5, 1.2 Hz, 1H), 1.03 (td, J=7.9, 3.0 Hz, 6H), 0.65 (dddt, J=12.6, 8.1, 6.5, 3.0 Hz, 4H); .sup.13C NMR (150 MHz, CDCl.sub.3) δ 140.3, 128.5, 127.3, 126.5, 125.6, 121.4, 41.1, 32.3, 25.6, 25.2, 20.5, 17.2, 8.6, 8.5, 2.0, 1.9; .sup.29Si NMR (120 MHz, CDCl.sub.3) δ 0.63; IR (cm.sup.−1) 2952, 2094, 1495, 1326, 1265, 1248, 1234, 1008, 856, 806; HRMS (EI): Calculated for C.sub.16H.sub.27NSi [M].sup.+: 261.1913, Found: 261.1913.

[Example 20] Preparation of 6-bromo-3-(diethylsilyl)-3-methyl-1,2,3,4-tetrahydroquinoline (22b)

[0185] ##STR00038##

[0186] 6-bromo-3-(diethylsilyl)-3-methyl-1,2,3,4-tetrahydroquinoline (22b) (yield: 76%) was obtained by the same method as Example 1 above except for using 6-bromo-3-methylquinoline (22a) instead of quinoline (1a) and stirring for 12 hours.

[0187] Colorless oil; .sup.1H NMR (600 MHz, CDCl.sub.3) δ 7.02 (d, J=2.6 Hz, 2H), 6.32 (d, J=9.1 Hz, 1H), 3.82 (br, 1H), 3.47 (dd, J=4.6, 2.4 Hz, 1H), 3.26 (dd, J=11.4, 1.1 Hz, 1H), 2.94 (dd, J=11.6, 1.6 Hz, 1H), 2.81 (d, J=16.3 Hz, 1H), 2.39 (d, J=16.3 Hz, 1H), 1.14-0.82 (m, 9H), 0.63 (ddd, J=8.2, 6.5, 4.0 Hz, 4H); .sup.13C NMR (150 MHz, CDCl.sub.3) δ 143.01, 132.1, 129.2, 122.0, 115.1, 108.1, 49.7, 36.7, 20.7, 18.9, 8.9, 8.8, 0.8, 0.5; .sup.29Si NMR (120 MHz, CDCl.sub.3) δ 6.59; IR (cm.sup.−1) 3429, 2953, 2915, 2874, 2098, 1640, 1493, 1460, 1376, 1302, 1276, 1236, 1084, 969, 802; HRMS (ESI): Calculated for C.sub.14H.sub.23BrNSi [M+H].sup.+: 314.0763, Found: 314.0750.

[Example 21] Preparation of 6-bromo-3-(diethylsilyl)-8-fluoro-1,2,3,4-tetrahydroquinoline (23b)

[0188] ##STR00039##

[0189] 6-bromo-3-(diethylsilyl)-8-fluoro-1,2,3,4-tetrahydroquinoline (23b) (yield: 90%) was obtained by the same method as Example 1 above except for using 6-bromo-8-fluoroquinoline (23a) instead of quinoline (1a) and stirring for 12 hours.

[0190] Colorless oil; .sup.1H NMR (600 MHz, CDCl.sub.3) δ 6.94 (dd, J=10.5, 2.1 Hz, 1H), 6.86 (dd, J=2.4, 1.2 Hz, 1H), 4.08 (s, br, 1H), 3.63 (q, J=3.1 Hz, 1H), 3.45 (ddd, J=11.6, 3.6, 1.8 Hz, 1H), 3.20 (t, J=11.5 Hz, 1H), 2.76 (ddd, J=16.6, 4.8, 1.8 Hz, 1H), 2.68 (dd, J=16.4, 11.8 Hz, 1H), 1.48-1.33 (m, 1H), 1.03 (ddd, J=8.6, 7.6, 1.2 Hz, 6H), 0.74-0.58 (m, 4H); .sup.13C NMR (150 MHz, CDCl.sub.3) δ 150.5 (d, J=242.1 Hz), 132.2 (d, J=11.9 Hz), 126.8 (d, J=3.0 Hz), 125.3 (d, J=4.4 Hz), 115.6 (d, J=21.6 Hz), 105.9, 43.2, 28.7 (d, J=3.0 Hz), 17.1, 8.3 (2C), 1.3, 1.2; .sup.29Si NMR (120 MHz, CDCl.sub.3) δ 0.28; .sup.19F NMR (564 MHz, CDCl.sub.3) δ −136.8 (d, J=10.5 Hz); IR (cm.sup.−1) 2952, 2873, 2831, 2096, 1499, 1306, 1279, 1232, 1207, 991, 842, 806; HRMS (EI): Calculated for C.sub.13H.sub.19BrFNSi [M].sup.+: 315.0454, Found: 315.0451.

[Example 22] Preparation of 6-chloro-3-(diethylsilyl)-8-fluoro-1,2,3,4-tetrahydroquinoline (24b)

[0191] ##STR00040##

[0192] 6-chloro-3-(diethylsilyl)-8-fluoro-1,2,3,4-tetrahydroquinoline (24b) (yield: 89%) was obtained by the same method as Example 1 above except for using 6-chloro-8-fluoroquinoline (24a) instead of quinoline (1a) and stirring at 23° C. for 10 mins.

[0193] Colorless oil; .sup.1H NMR (600 MHz, CDCl.sub.3) δ 6.81 (dd, J=10.8, 2.3 Hz, 1H), 6.73 (dd, J=2.5, 1.3 Hz, 1H), 4.04 (s, 1H), 3.64 (q, J=3.1 Hz, 1H), 3.45 (ddd, J=11.6, 3.5, 1.8 Hz, 1H), 3.21 (t, J=11.5 Hz, 1H), 2.76 (ddd, J=16.5, 4.8, 1.8 Hz, 1H), 2.68 (dd, J=16.4, 11.8 Hz, 1H), 1.50-1.31 (m, 1H), 1.04 (td, J=7.9, 1.4 Hz, 6H), 0.69 (dddd, J=10.8, 7.9, 4.8, 2.6 Hz, 4H); .sup.13C NMR (150 MHz, CDCl.sub.3) (150.3 (d, J=241.0 Hz), 131.7 (d, J=12.1 Hz), 124.7 (d, J=4.7 Hz), 123.9 (d, J=2.9 Hz), 119.4 (d, J=10.4 Hz), 112.9 (d, J=21.9 Hz), 43.2, 28.7 (d, J=3.1 Hz), 17.1, 8.3 (2C), 1.3, 1.1; .sup.29Si NMR (120 MHz, CDCl.sub.3) δ 0.34; .sup.19F NMR (564 MHz, CDCl.sub.3) δ −136.9 (d, J=10.8 Hz); IR (cm.sup.−1) 2952, 2874, 2095, 1500, 1415, 1308, 1281, 1236, 992, 888, 843, 710; HRMS (EI): Calculated for C.sub.13H.sub.19ClFNSi [M].sup.+: 271.0959, Found: 271.0959.

[Example 23] Preparation of 6-bromo-3-(diethylsilyl)-5,7-difluoro-1,2,3,4-tetrahydroquinoline (25b)

[0194] ##STR00041##

[0195] 6-bromo-3-(diethylsilyl)-5,7-difluoro-1,2,3,4-tetrahydroquinoline (25b) (yield: 85%) was obtained by the same method as Example 1 above except for using 7-bromo-6,8-difluoroquinoline (25a) instead of quinoline (1a).

[0196] Colorless oil; .sup.1H NMR (600 MHz, CDCl.sub.3) δ 6.06 (dd, J=9.5, 1.1 Hz, 1H), 4.16 (s, br, 1H), 3.62 (q, J=3.1 Hz, 1H), 3.36 (ddd, J=11.7, 3.5, 1.9 Hz, 1H), 3.16 (t, J=11.5 Hz, 1H), 2.86 (ddt, J=16.5, 2.9, 1.4 Hz, 1H), 2.55-2.41 (m, 1H), 1.30 (ddd, J=11.4, 7.6, 4.1 Hz, 1H), 1.02 (td, J=7.9, 1.3 Hz, 6H), 0.85-0.57 (m, 4H); 13C NMR (150 MHz, CDCl.sub.3) δ 158.6 (dd, J=130.4, 6.9 Hz), 157.0 (dd, J=130.1, 7.1 Hz), 145.2 (dd, J=12.6, 10.5 Hz), 105.7 (dd, J=22.5, 2.9 Hz), 96.8 (dd, J=25.8, 2.3 Hz), 82.5 (t, J=25.3 Hz), 43.4, 21.8 (d, J=3.0 Hz), 16.2, 8.3 (2C), 1.3, 1.1; .sup.29Si NMR (120 MHz, CDCl.sub.3) δ 0.38; .sup.19F NMR (564 MHz, CDCl.sub.3) δ −111.4, −111.5; IR (cm.sup.−1) 2953, 1874, 2098, 1621, 1588, 1492, 1459, 1412, 1347, 1301, 1279, 1262, 1233, 1197, 1080, 1016, 806; HRMS (EI): Calculated for C.sub.13H.sub.18BrF.sub.2NSi [M].sup.+: 333.0360, Found: 333.0361.

[Example 24] Preparation of 3-(diethylsilyl)-1,2,3,4-tetrahydrobenzo[h]quinoline (26b)

[0197] ##STR00042##

[0198] B(C.sub.6F.sub.5).sub.3 (0.025 mmol, 5.0 mol %) was dissolved in chloroform (0.50 mL) in a 2.5 mL reaction vial, then diethylsilane (2.0 mmol, 4.0 eq) and benzo[h]quinoline (26a, 0.50 mmol, 1.0 eq) were sequentially added thereto. The reaction mixture was stirred at 65° C. for 6 hours, cooled to room temperature, and filtrated by passing through a silica gel pad with dichloromethane (15 mL). After decompression concentration of the filtrate, the residue was purified by silica gel column chromatography (EA/Hx=5/95) to obtain 3-(diethylsilyl)-1,2,3,4-tetrahydrobenzo[h] quinoline (26b) (yield: 94%).

[0199] Colorless oil; .sup.1H NMR (600 MHz, CDCl.sub.3) δ 7.78-7.73 (m, 1H), 7.70 (dd, J=8.1, 1.7 Hz, 1H), 7.44-7.38 (m, 2H), 7.19 (d, J=8.2 Hz, 1H), 7.13 (d, J=8.3 Hz, 1H), 4.44 (br, 1H), 3.71 (d, J=3.1 Hz, 1H), 3.66-3.58 (m, 1H), 3.37 (t, J=11.6 Hz, 1H), 3.01-2.85 (m, 2H), 1.64-1.43 (m, 1H), 1.08 (t, J=7.9 Hz, 6H), 0.83-0.65 (m, 4H); .sup.13C NMR (150 MHz, CDCl.sub.3) δ 138.8, 133.0, 128.5, 128.2, 124.8, 124.6, 123.3, 119.3, 116.8, 116.2, 44.5, 29.6, 17.6, 8.4 (2C), 1.4, 1.2; .sup.29Si NMR (120 MHz, CDCl.sub.3) δ 0.34; IR (cm.sup.−1): 3419, 3050, 2871, 2090, 1574, 1518, 1398, 1266, 1233, 1009, 789; HRMS (EI): Calculated for C.sub.17H.sub.23NSi [M].sup.+: 269.1600, Found: 269.1600.

[Example 25] Preparation of 2-(diethylsilyl)-1,2,3,4-tetrahydrobenzo[f] quinoline (27b)

[0200] ##STR00043##

[0201] 2-(diethylsilyl)-1,2,3,4-tetrahydrobenzo[f]quinoline (27b) (yield: 85%) was obtained by the same method as Example 24 above except for using benzo[f]quinoline (27a) instead of benzo[h]quinoline (26a).

[0202] Colorless oil; .sup.1H NMR (600 MHz, CDCl.sub.3) δ 7.87 (d, J=8.3 Hz, 1H), 7.78 (d, J=8.0 Hz, 1H), 7.60 (d, J=8.6 Hz, 1H), 7.54 (td, J=6.6, 3.3 Hz, 1H), 7.33 (dd, J=8.0, 6.6 Hz, 1H), 6.80 (d, J=8.7 Hz, 1H), 4.08-3.76 (br, 1H), 3.84 (d, J=3.1 Hz, 1H), 3.45 (ddd, J=11.4, 3.4, 1.8 Hz, 1H), 3.30 (t, J=11.4 Hz, 2H), 2.98 (dd, J=16.3, 11.7 Hz, 1H), 1.66 (dt, J=5.6, 3.1 Hz, 1H), 1.18 (dd, J=7.9, 3.8 Hz, 6H), 0.89-0.77 (m, 4H); .sup.13C NMR (150 MHz, CDCl.sub.3) δ 141.8, 133.2, 128.3, 127.6, 126.9, 126.1, 121.4, 120.9, 118.3, 111.8, 43.5, 24.7, 17.4, 8.4 (2C), 1.4, 1.2; .sup.29Si NMR (120 MHz, CDCl.sub.3) δ 0.83; IR (cm.sup.−1): 3399, 2951, 2872, 2092, 1621, 1518, 1259, 1242, 1013, 805, 741; HRMS (EI): Calculated for C.sub.17H.sub.23NSi [M].sup.+: 269.1600, Found: 269.1602.

[Example 26] Preparation of 6-bromo-3-(diethylsilyl)-4-methyl-1,2,3,4-tetrahydroquinoline (44b)

[0203] ##STR00044##

[0204] 6-bromo-3-(diethylsilyl)-4-methyl-1,2,3,4-tetrahydroquinoline (44b) (yield: 82%) was obtained by the same method as Example 1 above except for using 6-bromo-4-methylquinoline (44a) instead of quinoline (1a).

[0205] Colorless oil; .sup.1H NMR (600 MHz, CDCl.sub.3) δ 7.23-7.12 (m, 1H), 7.03 (d, J=8.5 Hz, 1H), 6.34 (d, J=8.5 Hz, 1H), 3.63-3.54 (m, 1H), 3.52-3.39 (m, 1H), 3.26-3.16 (m, 1H), 2.97-2.77 (m, 1H), 1.33 (dd, J=6.8, 1.5 Hz, 3H), 1.17 (d, J=2.0 Hz, 1H), 1.03-0.94 (m, 6H), 0.61 (dt, J=7.9, 3.9 Hz, 4H); .sup.13C NMR (150 MHz, CDCl.sub.3) (143.6, 131.4, 129.3, 128.8, 115.9, 108.6, 40.3, 32.2, 25.0, 24.7, 8.52, 8.46, 1.9, 1.8; .sup.29Si NMR (120 MHz, CDCl.sub.3) δ 0.06; IR (cm.sup.−1) 2954, 2872, 2100, 1494, 1465, 1301, 1275, 1260, 1233, 1166, 805; HRMS (EI): Calculated for C.sub.14H.sub.22BrNSi [M].sup.+: 311.0705, Found: 311.0703.

Example II: Preparation of Silylative-Reduced Tetrahydrobenzoquinoline Compound (Chemical Formula 1-5)

[Example 27] Preparation of 2-(diethylsilyl)-1,2,3,4-tetrahydrobenzo[f]quinoline (32b)

[0206] ##STR00045##

[0207] B(C.sub.6F.sub.5).sub.3 (0.025 mmol, 5.0 mol %) was dissolved in chloroform (0.50 mL) in a 2.5 mL reaction vial, then diethylsilane (4.0 mmol, 8.0 eq) and 1,5-naphthyridine (32a, 0.50 mmol, 1.0 eq) were sequentially added thereto. The reaction mixture was stirred at 65° C. for 24 hours, cooled to room temperature, and filtrated by passing through a silica gel pad with dichloromethane (15 mL). After decompression concentration of the filtrate, the residue was purified by silica gel column chromatography (EA/Hx=5/95) to obtain 2-(diethylsilyl)-1,2,3,4-tetrahydrobenzo[f]quinoline (32b) (yield: 34%).

[0208] Colorless oil; .sup.1H NMR (600 MHz, CDCl.sub.3) δ 7.81 (dd, J=4.6, 1.7 Hz, 1H), 6.85 (dd, J=8.1, 4.6 Hz, 1H), 6.68 (dd, J=7.7, 1.7 Hz, 1H), 3.95 (br, 1H), 3.62 (d, J=3.1 Hz, 1H), 3.40-3.27 (m, 1H), 3.19 (t, J=11.5 Hz, 1H), 2.95 (ddd, J=17.1, 4.8, 2.1 Hz, 1H), 2.81 (dd, J=16.9, 12.2 Hz, 1H), 1.53-1.43 (m, 1H), 1.00 (t, J=8.0 Hz, 6H), 0.74-0.57 (m, 4H); .sup.13C NMR (150 MHz, CDCl.sub.3) δ 142.9, 140.6, 137.7, 121.8, 120.2, 43.6, 32.3, 17.3, 8.3, 8.2, 1.3, 1.0; .sup.29Si NMR (80 MHz, CDCl.sub.3) δ 0.21; IR (cm.sup.−1): 3314, 2953, 2874, 2099, 1583, 1556, 1451, 1368, 1259, 1233, 1006, 845, 727; HRMS (EI): Calculated for C.sub.12H.sub.20N.sub.2Si [M].sup.+: 220.1396, Found: 220.1394.

Example III: Preparation of Silvlative-Reduced Octahydro-Benzo-Phenanthroline Compound (Chemical Formula 1-6)

[Example 28] Preparation of 3,9-bis(diethylsilyl)-1,2,3,4,7,8,9,10-octahydro-1,7-phenanthroline (33b)

[0209] ##STR00046##

[0210] B(C.sub.6F.sub.5).sub.3 (0.005 mmol, 1.0 mol %) was dissolved in chloroform (0.50 mL) in a 2.5 mL reaction vial, then diethylsilane (4.0 mmol, 8.0 eq) and 1,7-phenanthroline (33a, 0.50 mmol, 1.0 eq) were sequentially added thereto. The reaction mixture was stirred at 65° C. for 6 hours, cooled to room temperature, and filtrated by passing through a silica gel pad with dichloromethane (15 mL). After decompression concentration of the filtrate, the residue was purified by silica gel column chromatography (EA/Hx=5/95) to obtain 3,9-bis(diethylsilyl)-1,2,3,4,7,8,9,10-octahydro-1,7-phenanthroline (33b) (yield: 72%).

[0211] Red oil; .sup.1H NMR (600 MHz, CDCl.sub.3) δ 6.68 (d, J=8.0 Hz, 1H), 5.97 (d, J=8.0 Hz, 1H), 3.69 (dd, J=16.1, 3.1 Hz, 2H), 3.63 (br, 2H), 3.51 (ddd, J=11.8, 3.4, 1.7 Hz, 1H), 3.32 (ddd, J=11.0, 3.1, 1.5 Hz, 1H), 3.27 (t, J=11.6 Hz, 1H), 3.15 (t, J=11.3 Hz, 1H), 2.80-2.68 (m, 2H), 2.48 (ddd, J=16.0, 5.9, 1.6 Hz, 1H), 2.34 (dd, J=15.9, 11.5 Hz, 1H), 1.56 (dddd, J=11.4, 8.5, 5.8, 2.9 Hz, 1H), 1.46 (dtd, J=11.2, 5.7, 3.0 Hz, 1H), 1.16-1.01 (m, 12H), 0.73 (ddd, J=9.1, 4.7, 1.8 Hz, 8H); .sup.13C NMR (150 MHz, CDCl.sub.3) δ 143.5, 141.9, 126.8, 111.2, 106.0, 104.4, 44.4, 43.3, 29.0, 23.3, 18.1, 17.9, 8.36, 8.33, 8.31 (2C), 1.4, 1.3, 1.19, 1.16; .sup.29Si NMR (120 MHz, CDCl.sub.3) δ 0.70, 0.33; IR (cm.sup.−1) 2952, 2873, 2825, 2093, 1609, 1488, 1336, 1240, 1123, 1012, 808; HRMS (EI): Calculated for C.sub.20H.sub.36N.sub.2Si.sub.2 [M].sup.+: 360.2417, Found: 360.2415.

Example IV: Preparation of Silvlative-Reduced Tetrahydroquinoline Compound (Chemical Formula 5-1)

[Example 29] Preparation of 8-{6-bromo-3-(diethylsilyl)-3,4-dihydroquinolin-1(2H)-ylsulfonyl}quinoline (13b-QUS)

[0212] ##STR00047##

[0213] B(C.sub.6F.sub.5).sub.3 (0.0050 mmol, 1.0 mol %) was dissolved in chloroform (0.50 mL) in a 2.5 mL reaction vial, then diethylsilane (2.0 mmol, 4.0 eq) and 6-bromoquinoline (13a, 0.50 mmol, 1.0 eq) were sequentially added thereto. The reaction mixture was stirred at 65° C. for 6 hours, cooled to room temperature, and filtrated by passing through a silica gel pad with dichloromethane (15 mL) and methanol (2 mL). After decompression concentration of the filtrate, dichloromethane (2 mL) was added to the residue, and in the presence of triethylamine (1.5 mmol, 3.0 eq), QUS-Cl (8-quinolinesulfonyl chloride, 0.75 mmol, 1.5 eq) was added thereto at 0° C. to room temperature. The reaction mixture was stirred at room temperature for 12 hours, followed by decompression concentration, and the obtained residue was purified by silica gel column chromatography (EA/Hx=3/7) to obtain 8-{6-bromo-3-(diethylsilyl)-3,4-dihydroquinolin-1(2H)-ylsulfonyl}quinoline (13b-QUS) (yield: 82%).

[0214] Colorless solid; m.p. 118-120° C.; .sup.1H NMR (600 MHz, CDCl.sub.3) δ 8.85 (dd, J=4.1, 1.9 Hz, 1H), 8.55 (dt, J=7.3, 1.4 Hz, 1H), 8.15 (dt, J=8.4, 1.8 Hz, 1H), 7.98 (dt, J=8.2, 1.5 Hz, 1H), 7.66-7.54 (m, 1H), 7.50 (d, J=8.9 Hz, 1H), 7.43 (dd, J=8.2, 4.2 Hz, 1H), 7.07 (dd, J=8.9, 2.3 Hz, 1H), 7.01 (d, J=2.5 Hz, 1H), 4.63 (ddd, J=12.6, 4.1, 1.7 Hz, 1H), 3.96 (t, J=12.8 Hz, 1H), 3.68 (q, J=3.1 Hz, 1H), 2.77-2.39 (m, 2H), 1.34 (dd, J=2.6, 1.4 Hz, 1H), 1.00 (q, J=8.1 Hz, 6H), 0.78-0.59 (m, 4H); .sup.13C NMR (150 MHz, CDCl.sub.3) δ 150.8, 143.7, 137.1, 136.3, 133.8, 133.5, 133.4, 131.6, 130.8, 129.0, 128.8, 125.2, 122.5, 122.0, 115.4, 49.5, 29.7, 18.9, 8.2, 8.19, 1.1, 1.0; .sup.29Si NMR (120 MHz, CDCl.sub.3) δ −0.20; IR (cm.sup.−1): 2953, 2135, 1478, 1338, 1208, 1166, 1143, 1026, 808, 781, 565; HRMS (EI): Calculated for C.sub.22H.sub.25BrN.sub.2O.sub.2SSi [M].sup.+: 488.0589, Found: 488.0592.

[Example 30] Preparation of 8-{6-bromo-3-(diethylsilyl)-2-methyl-3,4-dihydroquinolin-1(2H)-ylsulfonyl)}quinoline (18b-QUS)

[0215] ##STR00048##

[0216] 8-{6-bromo-3-(diethylsilyl)-2-methyl-3,4-dihydroquinolin-1(2H)-ylsulfonyl)}quinoline (18b-QUS) (yield: 49%) was obtained by the same method as Example 29 above except for using 6-bromo-2-methylquinoline (18a) instead of 6-bromoquinoline (13a).

[0217] Colorless solid; m.p. 152-154° C.; .sup.1H NMR (400 MHz, CDCl.sub.3) δ 8.72 (dd, J=4.1, 1.7 Hz, 1H), 8.55 (dd, J=7.5, 1.3 Hz, 1H), 8.15 (dd, J=8.3, 1.6 Hz, 1H), 8.00 (dd, J=8.2, 1.4 Hz, 1H), 7.69-7.55 (m, 2H), 7.46-7.36 (m, 1H), 7.19 (dd, J=9.0, 2.4 Hz, 1H), 7.13 (dd, J=2.5, 1.2 Hz, 1H), 4.99 (dd, J=6.9, 3.4 Hz, 1H), 3.56 (dq, J=3.6, 1.9 Hz, 1H), 2.71 (dd, J=17.5, 14.0 Hz, 1H), 2.48 (dd, J=17.6, 5.8 Hz, 1H), 1.19 (d, J=6.9 Hz, 4H), 0.93 (t, J=7.9 Hz, 3H), 0.81 (t, J=7.9 Hz, 3H), 0.68-0.49 (m, 4H); .sup.13C NMR (100 MHz, CDCl.sub.3) δ 150.8, 143.8, 137.1, 136.2, 135.1, 133.7, 132.9, 131.23, 129.3, 128.9, 128.8, 125.2, 125.1, 121.9, 115.9, 52.4, 24.9, 20.9, 16.7, 8.0, 7.8, 1.2, 0.9; .sup.29Si NMR (120 MHz, CDCl.sub.3) δ −0.72; IR (cm.sup.−1): 2954, 2872, 2085, 1477, 1332, 1228, 1162, 1144, 1005, 815, 784, 580; HRMS (ESI): Calculated for C.sub.23H.sub.27BrNaN.sub.2O.sub.2SSi [M+Na].sup.+: 525.0644, Found: 525.0653.

Example V: Preparation of Silvlative-Reduced Tetrahydroquinoline Compound (Chemical Formula 5-2)

[Example 31] Preparation of 8-{4-diethylsilyl)-3,4-dihydroisoquinolin-2(1H)-ylsulfonyl}quinoline (28b)

[0218] ##STR00049##

[0219] B(C.sub.6F.sub.5).sub.3 (0.005 mmol, 1.0 mol %) was dissolved in chloroform (0.50 mL) in a 2.5 mL reaction vial, then diethylsilane (4.0 mmol, 8.0 eq) and isoquinoline (28a, 0.50 mmol, 1.0 eq) were sequentially added thereto. The reaction mixture was stirred at 100° C. for 24 hours, cooled to room temperature, and filtrated by passing through a silica gel pad with dichloromethane (15 mL). After decompression concentration of the filtrate, dichloromethane (2 mL) was added to the residue, and in the presence of triethylamine (1.5 mmol, 3.0 eq), QUS-Cl (8-quinolinesulfonyl chloride, 0.75 mmol, 1.5 eq) was added thereto at 0° C. The reaction mixture was stirred at room temperature for 12 hours, followed by decompression concentration, and the obtained residue was purified by silica gel column chromatography (EA/Hx=3/7) to obtain 8-{4-diethylsilyl)-3,4-dihydroisoquinolin-2(1H)-ylsulfonyl}quinoline (28b) (yield: 44%).

[0220] White solid; m.p. 85-87° C.; .sup.1H NMR (400 MHz, CDCl.sub.3) δ 9.04 (dd, J=4.2, 1.8 Hz, 1H), 8.58 (dd, J=7.4, 1.4 Hz, 1H), 8.23 (dd, J=8.4, 1.9 Hz, 1H), 8.05 (dd, J=8.1, 1.4 Hz, 1H), 7.66 (t, J=7.8 Hz, 1H), 7.49 (dd, J=8.3, 4.2 Hz, 1H), 7.18-6.86 (m, 4H), 4.78 (d, J=15.4 Hz, 1H), 4.40 (d, J=15.4 Hz, 1H), 4.29 (dd, J=12.5, 3.1 Hz, 1H), 3.83 (d, J=3.1 Hz, 1H), 3.51 (dd, J=12.5, 4.1 Hz, 1H), 2.61 (d, J=3.2 Hz, 1H), 0.98 (t, J=7.8 Hz, 3H), 0.91 (t, J=7.8 Hz, 3H), 0.77 (td, J=7.5, 4.0 Hz, 4H); .sup.13C NMR (100 MHz, CDCl.sub.3) δ 151.1, 144.2, 136.7, 136.3, 136.3, 133.5, 133.4, 131.2, 128.8, 127.7, 126.3, 126.2, 125.4, 124.8, 121.9, 47.3, 46.3, 27.9, 8.3, 8.1, 1.89, 1.82; .sup.29Si NMR (120 MHz, CDCl.sub.3): δ 2.61; IR (cm.sup.−1): 2951, 2872, 2097, 1610, 1560, 1371, 1330, 1284, 1237, 1211, 1162, 1143, 1052, 868, 790; HRMS (FAB): Calculated for C.sub.22H.sub.27N.sub.2O.sub.2SSi [M+H].sup.+: 411.1563, Found: 411.1560.

[Example 32] Preparation of 8-{8-Bromo-4-(diethylsilyl)-3,4-dihydroisoquinolin-2(1H)-ylsulfonyl}quinoline (29b)

[0221] ##STR00050##

[0222] 8-{8-bromo-4-(diethylsilyl)-3,4-dihydroisoquinolin-2(1H)-ylsulfonyl}quinoline (29b) (yield: 66%) was obtained by the same method as Example 31 above except for using 8-bromoisoquinoline (29a) instead of isoquinoline (28a).

[0223] White solid; m.p. 99-101° C.; .sup.1H NMR (600 MHz, CDCl.sub.3) δ 9.00 (dd, J=4.1, 2.0 Hz, 1H), 8.64-8.46 (m, 1H), 8.19 (dd, J=8.4, 1.9 Hz, 1H), 8.08-7.90 (m, 1H), 7.61 (td, J=7.9, 3.0 Hz, 1H), 7.50-7.37 (m, 1H), 7.24 (d, J=7.7 Hz, 1H), 7.02-6.77 (m, 2H), 4.73 (d, J=16.4 Hz, 1H), 4.41-4.20 (m, 2H), 3.80 (q, J=3.2 Hz, 1H), 3.42 (dd, J=12.6, 3.9 Hz, 1H), 2.56 (t, J=3.4 Hz, 1H), 0.94 (dd, J=8.8, 7.1 Hz, 3H), 0.87 (t, J=7.9 Hz, 3H), 0.80-0.60 (m, 4H); .sup.13C NMR (150 MHz, CDCl.sub.3) δ 151.0, 144.1, 139.7, 136.3 (2C), 133.53, 133.47, 130.5, 128.8, 128.9, 127.3, 126.9, 125.4, 122.5, 121.9, 48.5, 45.9, 28.4, 8.3, 8.1, 1.8, 1.7; .sup.29Si NMR (120 MHz, CDCl.sub.3) δ 3.12; IR (cm.sup.−1): 2952, 2871, 2101, 1559, 1457, 1274, 1238, 1211, 1160, 953, 875, 787; HRMS (FAB): Calculated for C.sub.22H.sub.26BrN.sub.2O.sub.2SSi [M+H].sup.+: 489.0668, Found: 489.0666.

[Example 33] Preparation of 8-[{5-chloro-4-(diethylsilyl)-3,4-dihydroisoquinolin-2(1H)-yl}sulfonyl]quinoline (30b)

[0224] ##STR00051##

[0225] 8-[{5-chloro-4-(diethylsilyl)-3,4-dihydroisoquinolin-2(1H)-yl}sulfonyl]quinoline (30b) (yield: 81%) was obtained by the same method as Example 31 above except for using 5-chloroisoquinoline (30a) instead of isoquinoline (28a).

[0226] White solid; m.p. 129-131° C.; .sup.1H NMR (600 MHz, CDCl.sub.3) δ 9.02 (dd, J=4.2, 1.8 Hz, 1H), 8.56 (dd, J=7.4, 1.4 Hz, 1H), 8.21 (dd, J=8.3, 1.8 Hz, 1H), 8.03 (dd, J=8.2, 1.4 Hz, 1H), 7.65 (dd, J=8.2, 7.4 Hz, 1H), 7.48 (dd, J=8.3, 4.2 Hz, 1H), 7.21-7.11 (m, 1H), 6.97 (t, J=7.8 Hz, 1H), 6.94-6.85 (m, 1H), 4.82 (d, J=15.6 Hz, 1H), 4.48-4.33 (m, 2H), 3.81 (d, J=3.3 Hz, 1H), 3.31 (dd, J=12.1, 3.5 Hz, 1H), 3.04-2.95 (m, 1H), 0.94 (t, J=7.8 Hz, 3H), 0.87 (t, J=7.9 Hz, 3H), 0.81 (ddd, J=7.9, 7.0, 4.0 Hz, 1H), 0.76-0.68 (m, 1H), 0.65 (ddt, J=14.9, 8.1, 3.7 Hz, 2H); .sup.13C NMR (150 MHz, CDCl.sub.3) δ 151.2, 144.3, 136.4, 136.3, 136.2, 133.9, 133.54, 133.52, 132.4, 129.0, 127.4, 125.6, 125.5, 125.0, 122.0, 47.0, 46.6, 26.5, 8.4, 8.2, 2.9, 2.3; .sup.29Si NMR (120 MHz, CDCl.sub.3) δ 1.30; IR (cm.sup.−1) 2952, 2872, 2117, 1332, 1256, 1238, 1212, 1163, 833, 790, 586; HRMS (EI): Calculated for C.sub.22H.sub.25ClN.sub.2O.sub.2SSi [M].sup.+: 444.1095, Found: 444.1092.

[Example 34] Preparation of 8-[{5-Bromo-4-(diethylsilyl)-3,4-dihydroisoquinolin-2(1H)-yl}sulfonyl]quinoline (31b)

[0227] ##STR00052##

[0228] 8-[{5-bromo-4-(diethylsilyl)-3,4-dihydroisoquinolin-2(1H)-yl}sulfonyl]quinoline (31b) (yield: 71%) was obtained by the same method as Example 31 above except for using 5-bromoisoquinoline (31a) instead of isoquinoline (28a).

[0229] Semi-solid; .sup.1H NMR (600 MHz, CDCl.sub.3) δ 9.01 (dd, J=4.2, 1.8 Hz, 1H), 8.55 (dd, J=7.3, 1.5 Hz, 1H), 8.20 (dd, J=8.4, 1.8 Hz, 1H), 8.02 (dd, J=8.3, 1.5 Hz, 1H), 7.64 (t, J=7.8 Hz, 1H), 7.47 (dd, J=8.3, 4.2 Hz, 1H), 7.33 (dd, J=7.8, 1.3 Hz, 1H), 6.94 (dd, J=7.8, 1.4 Hz, 1H), 6.88 (t, J=7.8 Hz, 1H), 4.81 (d, J=15.6 Hz, 1H), 4.42 (d, J=15.6 Hz, 1H), 4.37 (dd, J=12.0, 2.0 Hz, 1H), 3.84 (d, J=3.3 Hz, 1H), 3.31 (dd, J=12.0, 3.5 Hz, 1H), 2.99 (d, J=2.7 Hz, 1H), 0.93 (t, J=7.8 Hz, 3H), 0.88 (t, J=7.9 Hz, 3H), 0.86-0.60 (m, 4H); .sup.13C NMR (150 MHz, CDCl.sub.3) δ 151.1, 144.2, 137.8, 136.4, 136.2, 133.8, 133.7, 133.5, 130.8, 128.9, 126.0, 125.7, 125.5, 123.4, 122.0, 47.0, 46.6, 29.1, 8.4, 8.2, 2.9, 2.3; .sup.29Si NMR (120 MHz, CDCl.sub.3) δ 1.07; IR (cm.sup.−1) 2871, 2118, 1561, 1493, 1437, 1332, 1239, 1221, 1191, 1162, 1147, 1070, 1052, 832, 789, 586; HRMS (EI): Calculated for C.sub.22H.sub.25ClN.sub.2O.sub.2SSi [M].sup.+: 488.0589, Found: 488.0588.

Example VI: Preparation of Silylative-Reduced Piperidine Compound (Chemical Formula 5-3)

[Example 35] Preparation of 5-(diethylsilyl)-2-methyl-1-(4-nitrophenylsulfonyl)piperidine (34b)

[0230] ##STR00053##

[0231] B(C.sub.6F.sub.5).sub.3 (0.025 mmol, 5.0 mol %) was dissolved in chloroform (0.50 mL) in a 2.5 mL reaction vial, then diethylsilane (4.0 mmol, 8.0 eq) and 2-methylpyridine (34a, 0.50 mmol, 1.0 eq) were sequentially added thereto. The reaction mixture was stirred at 100° C. for 12 hours, cooled to room temperature, and filtrated by passing through a silica gel pad with dichloromethane (15 mL). After decompression concentration of the filtrate, dichloromethane (2 mL) was added to the residue, and in the presence of triethylamine (1.5 mmol, 3.0 eq), NOS-Cl (4-nitrobenzenesulfonyl chloride, 0.75 mmol, 1.5 eq) was added thereto at 0° C. The reaction mixture was stirred at room temperature for 12 hours, followed by decompression concentration, and the obtained residue was purified by silica gel column chromatography (EA/Hx=3/7) to obtain 5-(diethylsilyl)-2-methyl-1-(4-nitrophenylsulfonyl)piperidine (34b) (yield: 72%).

[0232] Colorless solid; m.p. 51-53° C.; .sup.1H NMR (600 MHz, CDCl.sub.3) δ 8.32 (d, J=8.8 Hz, 2H), 7.97 (d, J=8.8 Hz, 2H), 3.91-3.68 (m, 1H), 3.67-3.47 (m, 2H), 3.27 (dd, J=12.6, 6.0 Hz, 1H), 1.82 (d, J=3.7 Hz, 2H), 1.55-1.36 (m, 2H), 1.22 (td, J=5.3, 4.4, 2.2 Hz, 1H), 1.11 (d, J=6.8 Hz, 3H), 0.95 (q, J=8.2 Hz, 6H), 0.70-0.53 (m, 4H); .sup.13C NMR (150 MHz, CDCl.sub.3) δ 149.7, 146.4, 128.3 (2C), 124.1 (2C), 51.4, 45.0, 31.0, 21.5, 20.6, 17.4, 8.2, 8.1, 1.3, 1.2; .sup.29Si NMR (120 MHz, CDCl.sub.3) δ −2.90; IR (cm.sup.−1): 2950, 2873, 2099, 1529, 1348, 1234, 1209, 1166, 854, 803, 689; HRMS (ESI): Calculated for C.sub.16H.sub.27N.sub.2O.sub.4SSi [M+H].sup.+: 371.1461, Found: 371.1459.

Example VII: Preparation of Silylative-Reduced Tetrahydroquinoline Compound (Chemical Formula 5-4)

[Example 36] Preparation of (6-bromo-2-methyl-1,2,3,4-tetrahydroquinolin-3-yl)diethylsilanol (18b)

[0233] ##STR00054##

[0234] B(C.sub.6F.sub.5).sub.3 (0.0050 mmol, 1.0 mol %) was dissolved in chloroform (0.50 mL) in a 2.5 mL reaction vial, then diethylsilane (4.0 mmol, 8.0 eq) and 6-bromo-2-methylquinoline (18a, 0.50 mmol, 1.0 eq) were sequentially added thereto. The reaction mixture was stirred at 65° C. for 12 hours, cooled to room temperature, and filtrated by passing through a silica gel pad with dichloromethane (15 mL) and methanol (2 mL). After decompression concentration of the filtrate, acetonitrile (3.0 mL) was added to the residue, and [Ru(p-cymene)Cl.sub.2].sub.2 (0.025 mmol, 5.0 mol %) and deionized water (10 mmol, 20 eq) were added thereto. The reaction mixture was stirred at 80° C. for 6 hours, followed by decompression concentration, and the obtained residue was purified by silica gel column chromatography (EA/Hx=3/7) to obtain (6-bromo-2-methyl-1,2,3,4-tetrahydroquinolin-3-yl)diethylsilanol (18b) (yield: 58%).

[0235] Colorless oil; .sup.1H NMR (600 MHz, CDCl.sub.3) δ 6.85 (dt, J=8.1, 1.0 Hz, 1H), 6.56 (dd, J=8.1, 2.1 Hz, 1H), 6.44 (d, J=2.1 Hz, 1H), 3.68 (dd, J=6.6, 3.3 Hz, 1H), 2.77 (d, J=7.5 Hz, 2H), 1.38 (td, J=7.5, 3.3 Hz, 1H), 1.25 (d, J=6.6 Hz, 3H), 0.99 (t, J=8.0 Hz, 3H), 0.95 (t, J=8.0 Hz, 3H), 0.74-0.56 (m, 4H); .sup.13C NMR (150 MHz, CDCl.sub.3) δ 144.9, 131.9, 130.0, 119.8, 116.9, 114.1, 48.2, 25.2, 24.8, 20.8, 6.6, 6.5, 6.3, 5.7; .sup.29Si NMR (120 MHz, CDCl.sub.3) δ 17.04; IR (cm.sup.−1): 3392, 3351, 2955, 2875, 1599, 1491, 1267, 1239, 1207, 1005, 821, 719; HRMS (EI): Calculated for C.sub.14H.sub.22BrNOSi [M].sup.+: 327.0654, Found: 327.0653.

[Example 37] Preparation of (2,8-dimethyl-1,2,3,4-tetrahydroquinolin-3-yl)diethylsilanol (19b)

[0236] ##STR00055##

[0237] (2,8-dimethyl-1,2,3,4-tetrahydroquinolin-3-yl)diethylsilanol (19b) (yield: 55%) was obtained by the same method as Example 36 above except for using 2,8-dimethylquinoline (19a) instead of 6-bromo-2-methylquinoline (18a).

[0238] Colorless oil; .sup.1H NMR (400 MHz, CDCl.sub.3) δ 6.92 (td, J=6.0, 2.7 Hz, 2H), 6.63 (t, J=7.4 Hz, 1H), 3.82 (dd, J=6.7, 3.2 Hz, 1H), 2.92 (dd, J=12.1, 7.0 Hz, 2H), 2.11 (s, 3H), 1.52-1.42 (m, 1H), 1.40-1.33 (d, J=7.9 Hz, 3H), 1.10-1.01 (m, 3H), 0.97 (t, J=7.9 Hz, 3H), 0.80-0.55 (m, 4H); .sup.13C NMR (100 MHz, CDCl.sub.3) δ 141.9, 127.9, 127.0, 121.8, 121.2, 117.0, 49.2, 26.7, 24.8, 21.4, 17.2, 6.7, 6.6, 6.5, 5.7; .sup.29Si NMR (120 MHz, CDCl.sub.3) δ 17.78; IR (cm.sup.−1): 3413, 2955, 2874, 1597, 1476, 1265, 1236, 1055, 754; HRMS (EI): Calculated for C.sub.15H.sub.25NOSi [M].sup.+: 263.1705, Found: 263.1704.

[Example 38] Preparation of (7-chloro-2-methyl-1,2,3,4-tetrahydroquinolin-3-yl)diethylsilanol (43b)

[0239] ##STR00056##

[0240] (7-chloro-2-methyl-1,2,3,4-tetrahydroquinolin-3-yl)diethylsilanol (43b) (yield: 67%) was obtained by the same method as Example 36 above except for using 7-chloro-2-methylquinoline (43a) instead of 6-bromo-2-methylquinoline (18a).

[0241] Colorless liquid; .sup.1H NMR (600 MHz, CDCl.sub.3) δ 7.07 (dd, J=2.2, 1.1 Hz, 1H), 7.03 (dd, J=8.5, 2.3 Hz, 1H), 6.34 (d, J=8.5 Hz, 1H), 3.67 (qd, J=6.6, 3.3 Hz, 1H), 2.79 (d, J=7.4 Hz, 2H), 1.36 (td, J=7.4, 3.2 Hz, 1H), 1.25 (d, J=6.6 Hz, 3H), 0.99 (t, J=8.0 Hz, 3H), 0.94 (t, J=7.9 Hz, 3H), 0.74-0.55 (m, 4H); .sup.13C NMR (150 MHz, CDCl.sub.3) (142.9, 131.5, 129.4, 123.6, 116.2, 108.8, 48.5, 25.7, 24.6, 20.8, 6.6, 6.5, 6.3, 5.7; .sup.29Si NMR (120 MHz, CDCl.sub.3) δ 17.06; IR (cm.sup.−1): 3397, 2955, 2914, 2876, 1601, 1579, 1493, 1314, 1268, 1241, 1088, 969, 724; HRMS (ESI): Calculated for C.sub.14H.sub.23ClNOSi [M+H].sup.+: 284.1237, Found: 284.1220.

Example VIII: Preparation of Silylative-Reduced N-Heterocyclic Compound (Chemical Formula 5-5)

[Example 39] Preparation of 1,2,2,4,4-pentamethyl-7-(quinolin-8-ylsulfonyl)-3-oxa-7-aza-2,4-disilabicyclo[3.3.1]nonane (38b)

[0242] ##STR00057##

[0243] B(C.sub.6F.sub.5).sub.3 (0.025 mmol, 5.0 mol %) was dissolved in chloroform (0.50 mL) in a 2.5 mL reaction vial, then 3-methyl pyridine (35a) was added thereto and stirred for 5 mins. Next, TMDS (tetramethyldisiloxane, 4.0 mmol, 8.0 eq) was added thereto and stirred at 100° C. for 24 hours. The reaction mixture was cooled to room temperature and filtrated by passing through a silica gel pad with dichloromethane (15 mL). After decompression concentration of the filtrate, triethylamine (1.5 mmol, 3.0 eq) and QUS-Cl (8-quinolinesulfonyl chloride, 0.75 mmol, 1.5 eq) were added thereto at 0° C. and stirred for 12 hours, then the residue obtained by decompression concentration was purified by silica gel column chromatography (EA/Hx=3/7) to obtain 1,2,2,4,4-pentamethyl-7-(quinolin-8-ylsulfonyl)-3-oxa-7-aza-2,4-disilabicyclo[3.3.1]nonane (38b) (yield: 43%) as a derivative having a silanol group introduced thereinto.

[0244] Colorless solid; m.p. 101-103° C.; .sup.1H NMR (600 MHz, CDCl.sub.3) δ 9.06 (dd, J=4.1, 1.8 Hz, 1H), 8.49 (dd, J=7.3, 1.2 Hz, 1H), 8.22 (dd, J=8.3, 1.8 Hz, 1H), 8.03 (dd, J=8.1, 1.4 Hz, 1H), 7.68-7.56 (m, 1H), 7.50 (dd, J=8.3, 4.2 Hz, 1H), 4.20 (dd, J=11.9, 1.8 Hz, 1H), 4.06 (d, J=11.8 Hz, 1H), 2.62 (dd, J=11.7, 3.5 Hz, 1H), 2.17-1.99 (m, 2H), 1.19 (d, J=4.8 Hz, 1H), 0.90 (dd, J=2.8, 1.3 Hz, 1H), 0.68 (s, 3H), 0.40 (s, 3H), 0.36 (s, 3H), 0.10 (s, 3H), 0.08 (s, 3H); .sup.13C NMR (150 MHz, CDCl.sub.3) δ 151.0, 144.5, 136.3, 135.7, 134.0, 133.4, 128.9, 125.4, 121.8, 57.6, 50.1, 36.1, 23.6, 23.4, 22.5, 0.0, −1.4, −1.6, −3.1; .sup.29Si NMR (120 MHz, CDCl.sub.3) δ 16.48, 13.47; IR (cm.sup.−1): 2953, 1491, 1460, 1333, 1297, 1251, 1162, 996, 825, 785; HRMS (FAB): Calculated for C.sub.19H.sub.29N.sub.2O.sub.3SSi.sub.2 [M+H].sup.+: 421.1435, Found: 421.1437.

[Example 40] Preparation of 1-butyl-2,2,4,4-tetramethyl-7-(quinolin-8-ylsulfonyl)-3-oxa-7-aza-2,4-disilabicyclo[3.3.1]nonane (39b)

[0245] ##STR00058##

[0246] 1-butyl-2,2,4,4-tetramethyl-7-(quinolin-8-ylsulfonyl)-3-oxa-7-aza-2,4-disilabicyclo[3.3.1]nonane (39b) was obtained by the same method as Example 39 above except for using 3-n-butyl pyridine (38a) instead of 3-methyl pyridine (35a).

[0247] Colorless oil; .sup.1H NMR (600 MHz, CDCl.sub.3): δ 9.06 (dd, J=4.2, 1.8 Hz, 1H), 8.49 (dd, J=7.4, 1.4 Hz, 1H), 8.23 (dd, J=8.4, 1.8 Hz, 1H), 8.03 (dd, J=8.2, 1.4 Hz, 1H), 7.63 (t, J=7.8 Hz, 1H), 7.50 (dd, J=8.3, 4.2 Hz, 1H), 4.34 (dt, J=12.0, 1.7 Hz, 1H), 4.24-4.07 (m, 1H), 2.56 (dd, J=11.6, 3.6 Hz, 1H), 2.09 (d, J=11.8 Hz, 1H), 2.04-1.96 (m, 1H), 1.37-1.13 (m, 5H), 1.13-1.05 (m, 1H), 0.86 (q, J=7.3, 6.4 Hz, 5H), 0.44 (s, 3H), 0.39 (s, 3H), 0.11 (s, 3H), 0.09 (s, 3H); .sup.13C NMR (150 MHz, CDCl.sub.3) δ 150.9, 144.6, 136.3, 135.6, 133.9, 133.4, 129.0, 125.5, 121.9, 56.2, 50.2, 39.1, 35.6, 27.5, 27.0, 23.6, 23.1, 13.8, 0.0, −0.2, −1.3, −1.6; .sup.29Si NMR (120 MHz, CDCl.sub.3) δ 16.93, 12.98; IR (cm.sup.−1): 2955, 1560, 1463, 1334, 1252, 1210, 1191, 1161, 996, 829, 782; HRMS (FAB): Calculated for C.sub.22H.sub.35N.sub.2O.sub.3SSi.sub.2 [M+H].sup.+: 463.1907, Found: 463.1904.

[Example 41] Preparation of 2,2,4,4-tetramethyl-1-phenyl-7-(quinolin-8-ylsulfonyl)-3-oxa-7-aza-2,4-disilabicyclo[3.3.1]nonane (40b)

[0248] ##STR00059##

[0249] 2,2,4,4-tetramethyl-1-phenyl-7-(quinolin-8-ylsulfonyl)-3-oxa-7-aza-2,4-disilabicyclo[3.3.1]nonane (40b) was obtained by the same method as Example 39 above except for using 3-phenyl pyridine (39a) instead of 3-methyl pyridine (35a).

[0250] White solid; m.p. 111-113° C.; .sup.1H NMR (600 MHz, CDCl.sub.3) δ 9.01 (dd, J=4.2, 1.8 Hz, 1H), 8.53 (dd, J=7.4, 1.4 Hz, 1H), 8.17 (dd, J=8.3, 1.8 Hz, 1H), 7.99 (dd, J=8.2, 1.4 Hz, 1H), 7.61 (t, J=7.8 Hz, 1H), 7.44 (dd, J=8.2, 4.2 Hz, 1H), 7.26 (dd, J=8.4, 7.2 Hz, 2H), 7.20-7.15 (m, 2H), 7.14-7.08 (m, 1H), 4.85 (dt, J=11.9, 1.8 Hz, 1H), 4.30-4.24 (m, 1H), 2.71 (dt, J=13.4, 2.2 Hz, 1H), 2.65 (dd, J=11.7, 3.5 Hz, 1H), 2.41 (d, J=11.9 Hz, 1H), 1.73 (dd, J=13.5, 5.0 Hz, 1H), 1.14-1.09 (m, 1H), 0.54 (s, 3H), 0.48 (s, 3H), 0.17 (s, 3H), −0.42 (s, 3H); .sup.13C NMR (150 MHz, CDCl.sub.3) δ 151.1, 144.7, 144.5, 136.2, 135.6, 134.0, 133.5, 128.9, 128.3 (2C), 125.4, 125.2, 125.2 (2C), 121.8, 55.6, 49.9, 33.5, 32.0, 23.2, 0.1, −1.2, −1.6, −2.9; .sup.29Si NMR (80 MHz, CDCl.sub.3) δ 13.46, 13.10; IR (cm.sup.−1): 2816, 1492, 1332, 1243, 1158, 1141, 1001, 829, 789, 759; HRMS (FAB): Calculated for C.sub.24H.sub.31N.sub.2O.sub.3SSi.sub.2 [M+H].sup.+: 483.1594, Found: 483.1597.

[Example 42] Preparation of 1-benzyl-1,2,3,4-tetrahydrobenzo[h]quinolin-3-ol (42)

[0251] ##STR00060##

[0252] Preparation of Compound 26b

[0253] B(C.sub.6F.sub.5).sub.3 (0.0080 mmol, 0.10 mol %) was dissolved in chloroform (3.0 mL) in a 15 mL sealed tube, then diethylsilane (32 mmol, 4.0 eq) was added thereto. A solution of compound 26a (8.0 mmol, 1.0 eq) dissolved in chloroform (5.0 mL) was added to the above-prepared solution. The reaction mixture was stirred at 65° C. for 12 hours, cooled to room temperature, and filtrated by passing through a silica gel pad with dichloromethane (50 mL) and methanol (5 mL). After decompression concentration of the filtrate, the obtained residue was purified by silica gel column chromatography (EA/Hx=5/95) to obtain a compound 26b (colorless oil, 2.0 g, 95%).

[0254] Preparation of Compound 41

[0255] A compound 26b (7.4 mmol, 1.0 eq) was dissolved in N,N-dimethylformamide (21 mL), then K.sub.2CO.sub.3 (22 mmol, 3.0 eq) and benzyl bromide (8.9 mmol, 1.2 eq) were dropwide added thereto at 0° C. for 10 mins. The reaction mixture was stirred at room temperature for 12 hours, and water (20 mL) was added thereto to thereby complete the reaction. Next, the reaction mixture was extracted with diethylether (20 mL×2), the obtained organic layer was washed with saturated ammonium chloride solution (40 mL), dried with anhydrous MgSO.sub.4, followed by filtration and decompression concentration, and the residue was purified by silica gel column chromatography (EA/Hx=1/10) to obtain a compound 41 (2.5 g, 95%).

[0256] Brown oil; .sup.1H NMR (600 MHz, CDCl.sub.3) δ 8.34-8.29 (m, 1H), 7.90-7.85 (m, 1H), 7.76-7.71 (m, 2H), 7.58-7.51 (m, 3H), 7.51-7.43 (m, 3H), 7.27 (d, J=8.4 Hz, 1H), 4.68 (d, J=16.1 Hz, 1H), 4.18 (d, J=16.0 Hz, 1H), 3.77 (q, J=3.1 Hz, 1H), 3.38 (ddd, J=13.7, 2.7, 1.5 Hz, 1H), 3.14 (ddd, J=13.8, 12.5, 1.5 Hz, 1H), 3.07-2.99 (m, 2H), 1.80 (dt, J=5.6, 2.7 Hz, 1H), 1.13 (dt, J=19.4, 7.9 Hz, 6H), 0.79 (dd, J=7.9, 3.2 Hz, 4H); .sup.13C NMR (150 MHz, CDCl.sub.3) δ 144.1, 139.5, 133.4, 128.9, 128.6 (2C), 128.3, 127.8, 127.4 (2C), 127.0, 125.7, 125.2, 124.9, 122.8, 122.0, 58.9, 49.0, 30.1, 11.2, 8.4, 8.3, 1.2, 1.1; .sup.29Si NMR (120 MHz, CDCl.sub.3) δ 0.16; IR (cm.sup.−1): 3047, 2950, 2871, 2090, 1601, 1569, 1451, 1395, 1359, 1028, 801; HRMS (EI): Calculated for C.sub.24H.sub.29NSi [M].sup.+: 359.2069, Found: 359.2067.

[0257] Preparation of Compound 42

[0258] A compound 41 (7.0 mmol, 1.0 eq), KF (42 mmol, 6.0 eq), KHCO.sub.3 (42 mmol, 6.0 eq), 30% aqueous hydrogen peroxide solution (130 mmol, 18 eq), and tetrahydrofuran (59 mL) were mixed with methanol (59 mL), and stirred at 60° C. for 12 hours. 10% NaHSO.sub.3 aqueous solution (20 mL) was added to the reaction mixture at 0° C., and extracted with diethylether (60 mL×3). The obtained organic layer was washed with saturated Na.sub.2CO.sub.3 aqueous solution (60 mL×2), dried with anhydrous MgSO.sub.4, followed by filtration and decompression concentration, and the residue was purified by silica gel column chromatography (EA/Hx=1/1) to obtain a compound 42 (1.8 g, 91%).

[0259] Colorless solid; m.p. 62-64° C.; .sup.1H NMR (600 MHz, CDCl.sub.3) δ 8.14-8.04 (m, 1H), 7.81 (d, J=7.7 Hz, 1H), 7.60 (d, J=7.6 Hz, 2H), 7.53-7.44 (m, 3H), 7.38 (d, J=8.0 Hz, 3H), 7.18 (d, J=8.4 Hz, 1H), 4.69 (d, J=16.3 Hz, 1H), 4.36-4.27 (m, 1H), 4.24 (d, J=16.3 Hz, 1H), 3.42-3.22 (m, 2H), 2.99 (dd, J=13.1, 9.8 Hz, 1H), 2.92-2.76 (m, 1H), 1.93-1.58 (m, 1H); .sup.13C NMR (150 MHz, CDCl.sub.3) δ 142.7, 139.2, 133.7, 128.7 (2C), 128.4, 128.0, 127.8, 127.2 (2C), 127.1, 125.4, 125.2, 123.1, 122.6, 122.5, 61.1, 60.0, 53.3, 37.6; IR (cm.sup.−1): 3337, 3050, 2922, 2836, 1569, 1463, 1452, 1397, 1052, 804, 733; HRMS (EI): Calculated for C.sub.20H.sub.19NO [M].sup.+: 289.1467, Found: 289.1464.

[Example 43] Preparation of (3S,4S)-4-((S)-1-Hydroxyethyl)-1,2,3,4-tetrahydroquinolin-3-ol (47)

Preparation of 1-(quinolin-4-yl)ethan-1-ol

[0260] ##STR00061##

[0261] 4-quinolinecarboxaldehyde (12 mmol, 1.0 eq) was added to tetrahydrofuran (60 mL) and stirred at 0° C., then 3.0 M methylmagnesium bromide solution in diethylether (13 mmol, 1.1 eq) was dropwise added thereto at room temperature. The reaction mixture was stirred at room temperature for 12 hours, and saturated ammonium chloride solution (20 mL) was added thereto to thereby complete the reaction. Then, water (40 mL) and ethyl acetate (30 mL) were added thereto, and extracted with ethyl acetate (60 mL×2). The obtained organic layer was dried with anhydrous MgSO.sub.4, followed by filtration and decompression concentration, and the residue was purified by silica gel column chromatography (EA/Hx=1/1) to obtain 1-(quinolin-4-yl)ethan-1-ol (1.8 g, 87%).

[0262] White solid; m.p. 119-121° C.; .sup.1H NMR (600 MHz, CDCl.sub.3) δ 8.70 (s, 1H), 8.05 (d, J=8.5 Hz, 1H), 7.98 (d, J=8.5 Hz, 1H), 7.64 (t, J=7.9 Hz, 1H), 7.55 (s, 1H), 7.50 (t, J=7.8 Hz, 1H), 5.63 (d, J=7.8 Hz, 1H), 1.62 (d, J=6.5 Hz, 3H); .sup.13C NMR (150 MHz, CDCl.sub.3) δ 151.9, 150.2, 147.8, 129.9, 129.0, 126.5, 125.3, 123.0, 116.7, 65.8, 24.6; IR (cm.sup.−1) 3349, 2976, 2928, 1666, 1592, 1510, 1239, 1168, 1121, 1073, 1017, 856, 763; HRMS (EI): Calculated for C.sub.11H.sub.11NO [M].sup.+: 173.0841, Found: 173.0841.

Preparation of (S)-1-(quinolin-4-yl)ethan-1-ol

[0263] ##STR00062##

[0264] Tetrahydrofuran (10 mL), vinyl acetate (40 mL) and racemic alcohol starting material (10 mmol, 1.0 eq) were mixed, and lipase A from Candida Antarctica, CLEA (≧1 U/mg, Sigma, 560 mg) was added thereto at room temperature. The reaction mixture was stirred under open flask condition for 8 hours, and filtrated. After decompression concentration of the obtained filtrate, the residue was purified by silica gel column chromatography (EA/Hx=1/1) to obtain (S)-1-(quinolin-4-yl)ethan-1-ol (560 mg, 31%, ee=98% based on HPLC).

[0265] .sup.1H NMR (600 MHz, CDCl.sub.3) δ 8.58 (d, J=4.6 Hz, 1H), 7.96 (dd, J=8.4, 1.3 Hz, 1H), 7.91 (dd, J=8.6, 1.4 Hz, 1H), 7.60-7.50 (m, 2H), 7.46-7.38 (m, 1H), 5.58 (q, J=6.5 Hz, 1H), 1.58 (d, J=6.6 Hz, 3H); ee determination condition:Chiralcel IF, Hexane:EtOH=90:10, Flow=1.0 ml/min; [α].sub.D.sup.25 −87.2 (c=1.19, CHCl.sub.3).

Preparation of (S)-4-[1-{(triisopropylsilyl)oxy}ethyl]quinoline ((S)-45a)

[0266] ##STR00063##

[0267] (S)-1-(quinolin-4-yl)ethan-1-ol (2.3 mmol, 1.0 eq) was added to N,N-dimethylformamide (6.0 mL), then imidazole (5.8 mmol, 2.5 eq) and triisopropylsilyl chloride (3.5 mmol, 1.5 eq) were added thereto at room temperature. The reaction mixture was stirred overnight, and water (6 mL) was added thereto to thereby complete the reaction, then extracted with diethylether (10 mL×3), and dried with anhydrous MgSO.sub.4, followed by filtration and decompression concentration, and the residue was purified by silica gel column chromatography (EA/Hx=1/10) to obtain (S)-4-[1-{(triisopropylsilyl)oxy}ethyl]quinoline ((S)-45a) which is a silylether compound (586 mg, 77%).

[0268] Colorless oil; .sup.1H NMR (600 MHz, CDCl.sub.3) δ 8.91 (d, J=4.3 Hz, 1H), 8.13 (d, J=8.4 Hz, 1H), 8.00 (d, J=8.4 Hz, 1H), 7.76-7.60 (m, 2H), 7.53 (t, J=7.7 Hz, 1H), 5.68 (d, J=6.3 Hz, 1H), 1.58 (d, J=6.1 Hz, 3H), 1.14 (d, J=7.7 Hz, 3H), 1.06 (dd, J=7.3, 3.2 Hz, 9H), 1.05-0.95 (m, 9H); .sup.13C NMR (150 MHz, CDCl.sub.3) δ 152.5, 150.5, 148.2, 130.3, 128.8, 126.2, 125.0, 122.9, 117.3, 67.3, 26.7, 18.0 (6C), 12.2 (3C); IR (cm.sup.−1) 2942, 2865, 1592, 1509, 1462, 1369, 1297, 1239, 1208, 1168, 1121, 1091, 1038, 947, 881, 845, 758, 724, 678, 559, 451; HRMS (FAB): Calculated for C.sub.20H.sub.32NOSi [M+H].sup.+: 330.2253, Found: 330.2251.

Preparation of (3R,4S)-3-(diethylsilyl)-4-[(S)-1-{(triisopropylsilyl)oxy}ethyl]-1,2,3,4-tetrahydroquinoline (45b)

[0269] ##STR00064##

[0270] B(C.sub.6F.sub.5).sub.3 (0.0050 mmol, 1.0 mol %) was dissolved in chloroform (0.25 mL) in a 2.5 mL reaction vial, then diethylsilane (4.4 mmol, 8.0 eq) was added thereto. A quinoline compound (S)-45a (0.55 mmol, 1.0 eq) dissolved in chloroform (0.3 mL) was added to the above-prepared solution, and stirred at 100° C. for 12 hours, cooled to room temperature, and filtrated by passing through a silica gel pad with dichloromethane (15 mL) and methanol (2 mL). After decompression concentration of the filtrate, the residue was purified by silica gel column chromatography (EA/Hx=1/20) to obtain (3R,4S)-3-(diethylsilyl)-4-[(S)-1-{(triisopropylsilyl)oxy}ethyl]-1,2,3,4-tetrahydroquinoline (45b) (159 mg, 69%).

[0271] Colorless oil; .sup.1H NMR (600 MHz, CDCl.sub.3) δ 7.09 (dd, J=7.6, 1.5 Hz, 1H), 7.03-6.90 (m, 1H), 6.58 (td, J=7.4, 1.2 Hz, 1H), 6.43 (dd, J=8.0, 1.2 Hz, 1H), 4.14 (t, J=6.2 Hz, 1H), 3.86 (s, br, 1H), 3.66 (dd, J=11.3, 4.5 Hz, 1H), 3.48 (q, J=3.1 Hz, 1H), 3.22 (dd, J=11.4, 3.0 Hz, 1H), 2.67 (dd, J=6.4, 2.3 Hz, 1H), 1.85 (dd, J=4.6, 2.6 Hz, 1H), 1.22 (d, J=6.1 Hz, 3H), 1.04 (d, J=5.8 Hz, 21H), 0.99-0.89 (m, 6H), 0.66-0.46 (m, 4H); .sup.13C NMR (150 MHz, CDCl.sub.3) δ 145.3, 131.3, 127.1, 121.2, 116.3, 113.9, 72.4, 46.0, 40.3, 22.0, 18.24 (3C), 18.22 (3C), 17.3, 12.9 (3C), 8.42, 8.38, 1.8, 1.7; .sup.29Si NMR (120 MHz, CDCl.sub.3) δ 10.07, 1.44; IR (cm.sup.−1) 2943, 2866, 2089, 1607, 1501, 1462, 1371, 1351, 1315, 1274, 1258, 1236, 1121, 1058, 1002, 920, 882, 806, 744, 673, 495; HRMS (EI): Calculated for C.sub.24H.sub.45NOSi.sub.2 [M].sup.+: 419.3040, Found: 419.3036; [α].sub.D.sup.25 −18.9 (c=1.0, CHCl.sub.3).

Preparation of (3S,4S)-4-((S)-1-Hydroxyethyl)-1,2,3,4-tetrahydroquinolin-3-ol (47)

[0272] ##STR00065##

[0273] A compound 45b (0.35 mmol, 1.0 eq), triethylamine (0.88 mmol, 2.5 eq), 3,5-dinitrobenzoyl chloride (0.53 mmol, 1.5 eq) and 4-(dimethylamino)-pyridine (0.18 mmol, 0.50 eq) were sequentially added to dichloromethane (3.0 mL) at room temperature, and stirred at room temperature for 2 hours. Saturated aqueous NaHCO.sub.3 solution (4 mL) was added thereto to thereby complete the reaction, and extracted with ethyl acetate (4 mL×3). The obtained organic layer was dried with anhydrous MgSO.sub.4, followed by filtration and decompression concentration, and the residue was purified by silica gel column chromatography (EA/Hx=1/10) to obtain corresponding amide product (step i).

[0274] Tetrahydrofuran (1.5 mL) and methanol (1.5 mL) were added to the obtained amide product (0.29 mmol, 1.0 eq), then KF (0.87 mmol, 3.0 eq), KHCO.sub.3 (0.87 mmol, 3.0 eq) and 30% aqueous hydrogen peroxide solution (2.6 mmol, 9.0 eq) were added thereto at room temperature. The reaction mixture was stirred at 60° C. for 8 hours, then saturated Na.sub.2SO.sub.3 aqueous solution (5 mL) was added thereto to thereby complete the reaction. Next, the reaction mixture was extracted with ethyl acetate (5 mL×3), the obtained organic layer was dried with anhydrous MgSO.sub.4, followed by filtration and decompression concentration, and the residue was purified by silica gel column chromatography (EA/Hx=1/1) to obtain a corresponding secondary alcohol product 46 as a white solid (ee=98% based on HPLC) (step ii).

##STR00066##

ee determination condition: Chiralcel ID, Hexane:IPA=80:20, Flow=1.0 ml/min.

[0275] The obtained secondary alcohol product 46 (0.092 mmol, 1.0 eq) was added to tetrahydrofuran (1.0 mL), then 1.0 M tetrabutylammonium fluoride solution in tetrahydrofuran (0.14 mmol, 1.5 eq) was added thereto at room temperature. The reaction mixture was stirred at room temperature for 16 hours, followed by decompression concentration. The residue was purified by silica gel column chromatography (EA) to obtain a corresponding diol product 47 (step iii) (6.2 mg, 35% in 3 steps).

[0276] White solid; m.p. 143-145° C.; .sup.1H NMR (600 MHz, CD.sub.3OD) δ 7.00 (dd, J=7.6, 1.5 Hz, 1H), 6.98-6.90 (m, 1H), 6.57-6.46 (m, 2H), 4.35 (d, J=3.2 Hz, 1H), 3.69 (dd, J=8.2, 6.3 Hz, 1H), 3.44 (dd, J=12.6, 2.7 Hz, 1H), 3.26-3.18 (m, 1H), 2.65 (ddd, J=8.3, 3.4, 1.6 Hz, 1H), 1.18 (d, J=6.3 Hz, 3H); .sup.13C NMR (100 MHz, CD.sub.3OD) δ 145.9, 133.0, 128.5, 120.0, 117.2, 115.0, 71.3, 64.5, 53.51, 45.5, 22.1; IR (cm.sup.−1) 3302, 1603, 1580, 1500, 1370, 1319, 1284, 1253, 1225, 1127, 1105, 1056, 1020, 929, 875, 784, 744, 723, 655, 510; HRMS (ESI): Calculated for C.sub.11H.sub.16NO.sub.2 [M+H].sup.+: 194.1176, Found: 194.1153.