Functionalized cyanosilane and synthesis method and use thereof

Abstract

The present teachings relate to a functionalized silyl cyanide and synthetic methods thereof. As an example, the method may include adding a raw material silane and a cyanide source MCN in an organic solvent to produce the functionalized silyl cyanide in the absence of catalyst or in the presence of a metal salt catalyst. The functionalized silyl cyanide may be used in the reactions that classic TMSCN participates in, to synthesize important intermediates (e.g., cyanohydrin, amino alcohols and -amino nitrile compounds), with improved reactivity and selectivity. The cyanosilyl ether resulted from the nucleophilic addition of functionalized silyl cyanide to aldehyde or ketone may undergo intramolecular reaction under appropriate conditions to transfer the functional groups on silicon onto the other parts of the product linked to silicon. Such a functional group transfer process may increase the synthesis efficiency and atom economy, as well as afford products unobtainable using traditional TMSCN.

Claims

1. A functionalized silyl cyanide having the following formula (1): ##STR00198## wherein, FG is selected from F, Cl, Br, I, CHF.sub.2, CHCl.sub.2, CH.sub.2CHCR.sub.2, CHCR.sub.2 and CCR; wherein, CH.sub.2CHCR.sub.2, CHCR.sub.2 and CCR are functional groups having unsaturated carbon-carbon bond, wherein, R is H, Me; R.sup.1 is Me, Et; n=1-5; wherein when n=1 and each R.sup.1 is Me, FG is not CHCH.sub.2.

2. A compound, having the following structural Formula (7), ##STR00199## wherein, Z is Cl, Br.

Description

DETAILED DESCRIPTION

(1) In the following detailed description, numerous specific details are set forth by way of examples in order to provide a thorough understanding of the relevant teachings. However, it should be apparent to those skilled in the art that the present teachings may be practiced without such details. In other instances, well known methods, procedures, components, and/or circuitry have been described at a relatively high-level, without detail, in order to avoid unnecessarily obscuring aspects of the present teachings.

(2) The present disclosure generally relates to systems, methods, medium, and other implementations directed a series of novel functionalized silyl cyanide 1 are designed and synthesized in the present invention. In principle, the functionalized silyl cyanide 1 could participate in all reactions which could be realized by TMSCN. In principle, the functionalized silyl cyanide 1 could participate in all reactions which could be realized by TMSCN. In addition, the functionalized silyl cyanide 1 also has the following three advantages:

(3) First, the introduction of the functional group (FG) has certain influence on the steric and electrical property of the silicon atom, and makes the functionalized silyl cyanide 1 more reactive or selective than TMSCN.

(4) ##STR00017##

(5) In nucleophilic addition reaction of the functionalized silyl cyanide 1 to carbonyl compounds, the adduct could occur intramolecular reaction under appropriate conditions, to transfer the functional groups on the silyl into the final product. It not only enables the utilization of the functional groups on the silyl, thus improves the overall atomic utilization of the reaction, but also realizes the conversions which are difficult to be achieved in intermolecular fashion.

(6) The invention now being generally described, it will be more readily understood by reference to the following examples which are included merely for purpose of illustration of certain aspects and examples of the present invention, and are not intended to limit the invention.

(7) 1) Conversion from Compound 2a to Compound 1aaa (Table 1)

(8) ##STR00018##

(9) General procedure 1: a newly distilled 2a (100-300 mmol), MCN (150-300 mmol), a catalyst NX.sup.1.sub.a (3-9 mmol) and an organic solvent (100 mL) were added into a dry three-necked flask (250 mL). The mixture was stirred at a temperature shown in Table 1. The progress of the reaction was monitored by GC analysis. After the consumption of the raw material 2a was complete, 1aaa as shown in Scheme (Ia) was obtained through reduced pressure distillation.

(10) The specific experimental operations of the examples 1-17 are referred to general procedure 1. The specific reaction conditions and yield of each example are shown in Table 1. Wherein, 2a in Scheme (Ia) represents 2aa-2ad in Table 1 respectively.

(11) TABLE-US-00001 TABLE 1 Specific reaction conditions and yields of the examples 1-17. 2a (X) (mmol)/MCN Temperature Time Yield Example (mmol)/NX.sup.1.sub.a (mmol) Solvent ( C.) (h) (%) 1 2aa Cl (150)/HCN (200)/KI THF 0 48 66 (6) 2 2aa Cl (150)/LiCN (200)/KI toluene 150 36 37 (6) 3 2aa Cl (150)/NaCN (200)/KI THF 80 24 68 (6) 7 2aa Cl (150)/NaCN (200)/LiI DMA 150 36 34 (6) 8 2aa Cl (100)/NaCN (150)/NaI THF 100 36 66 (6) 9 2aa Cl (100)/NaCN THF 80 36 37 (150)/MgI.sub.2 (6) 10 2aa Cl (100)/NaCN THF 80 36 74 (150)/ZnI.sub.2 (6) 11 2aa Cl (300)/NaCN (300)/KI DMF 120 72 67 (6) 12 2aa Cl (200)/NaCN (250)/KI DMF 120 72 73 (3) 13 2aa Cl (200)/NaCN (150)/KI DMF 20 30 40 (9) 14 2ab Br (100)/NaCN (150)/KI THF 80 34 68 (6) 15 2ac I (100)/NaCN (150)/KI THF 80 24 66 (6) 16 2ad OTf (100)NaCN THF 80 72 35 (150)/KI (6) 17 2ad OTf (100)NaCN CH.sub.3CN 25 48 65 (150)KI (6)

(12) The characterization of compound 1aaa is as follows:

(13) ##STR00019##

(14) .sup.1H NMR (400 MHz, CDCl.sub.3): 2.96 (s, 2H), 0.48 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 124.63, 26.94, 4.73;

(15) 2) Conversion from Compound 2 to Compound 1 (Table 2)

(16) ##STR00020##

(17) General procedure 2: a newly distilled halogenated silane 2 (150 mmol), NaCN (200 mmol), catalyst ZnI.sub.2 (6 mmol) and an organic solvent (100 mL) were added into a dry 250 mL three-necked flask. The mixture was stirred at a temperature shown in Table 2. The progress of the reaction was monitored by GC analysis. After the full consumption of the raw material halogenated silane 2, compound 1 as shown in Scheme (Ib) was obtained by reduced pressure distillation.

(18) The specific experimental operations of the examples 18-37 are referred to general procedure 2. The specific reaction conditions and yield of each example are shown in Table 2. Wherein, 2 in Scheme (Ib) represents 2b-2m in Table 2, and 1 represents 1aab-1abd in Table 2 respectively.

(19) TABLE-US-00002 TABLE 2 Specific reaction conditions and yields of the examples 18-37. Ex- Temper- Product/ am- ature Time Yield ple 2 Solvent ( C.) (h) (%) 18 THF 80 48 1aab/66 19 2b DMA 150 24 1aab/78 20 2b CH.sub.3CN 100 24 1aab/77 21 THF 80 36 1aba/67 22 2c DMA 150 36 1aba/34 23 2c CH.sub.3CN 100 36 1aba/37 24 THF 80 36 1abb/44 25 2d DMA 150 72 1abb/73 26 2d CH.sub.3CN 100 72 1abb/56 27 THF 80 34 1aca/68 28 2e DMA 150 72 1aca/35 29 2e CH.sub.3CN 100 48 1aca/77 30 CH.sub.3CN 100 48 1bba/75 31 CH.sub.3CN 80 48 1ada/42 32 CH.sub.3CN 80 24 1adb/71 33 CH.sub.3CN 80 24 1aea/74 34 CH.sub.3CN 80 24 1aeb/49 35 0 CH.sub.3CN 80 24 1abc/67 36 CH.sub.3CN 80 24 1aec/46 37 CH.sub.3CN 80 24 1abd/58

(20) The characterizations of 1aab-1abd are as follows:

(21) ##STR00033##

(22) .sup.1H NMR (400 MHz, CDCl.sub.3): 3.3 (s, 2H), 0.38 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 128.23, 27.89, 4.78;

(23) ##STR00034##

(24) .sup.1H NMR (400 MHz, CDCl.sub.3): 5.42 (d, 1H), 5.36 (s, 1H), 5.16 (d, 1H), 0.40 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 138.0, 124.9, 118.9, 4.05;

(25) ##STR00035##

(26) .sup.1H NMR (400 MHz, CDCl.sub.3): 5.35 (dd, 1H), 5.24 (m, 2H), 2.08 (t, 2H), 0.43 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 135.0, 121.7, 119.8, 12.9, 4.09;

(27) ##STR00036##

(28) .sup.1H NMR (400 MHz, CDCl.sub.3): 4.96 (s, 1H), 0.58 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 128.6, 56.7, 6.73.

(29) ##STR00037##

(30) .sup.1H NMR (400 MHz, CDCl.sub.3): 5.14 (dd, 1H), 5.05 (m, 2H), 0.78 (t, 6H), 0.43 (q, 4H); .sup.13C NMR (100 MHz, CDCl.sub.3): 128.0, 115.7, 110.1, 12.9, 3.78;

(31) ##STR00038##

(32) .sup.1H NMR (400 MHz, CDCl.sub.3): 5.4 (t, 1H), 1.37 (m, 2H), 0.08 (d, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 117.8, 115.5, 22.1, 2.6;

(33) ##STR00039##

(34) .sup.1H NMR (400 MHz, CDCl.sub.3): 5.3 (t, 1H), 1.36 (m, 2H), 0.08 (d, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 116.8, 112.6, 25.1, 2.7;

(35) ##STR00040##

(36) .sup.1H NMR (400 MHz, CDCl.sub.3): 2.81 (s, 1H), 0.13 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 117.3, 90.5, 89.5, 0.6;

(37) ##STR00041##

(38) .sup.1H NMR (400 MHz, CDCl.sub.3): 2.83 (s, 1H), 2.31 (t, 2H), 1.18 (t, 2H), 0.10 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 117.5, 86.2, 69.7, 13.9, 13.6, 2.8;

(39) ##STR00042##

(40) .sup.1H NMR (400 MHz, CDCl.sub.3): 5.22 (dd, 1H), 2.07 (d, 2H), 1.82 (m, 3H), 1.74 (d, 3H), 0.10 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 132.5, 120.3, 118.5, 28.0, 17.9, 11.4, 2.3;

(41) ##STR00043##

(42) .sup.1H NMR (400 MHz, CDCl.sub.3): 2.22 (t, 2H), 2.03 (s, 3H), 1.22 (t, 2H), 0.11 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 122.0, 83.3, 78.5, 14.0, 11.9, 3.7, 2.9;

(43) ##STR00044##

(44) .sup.1H NMR (400 MHz, CDCl.sub.3): 5.82 (dd, 1H), 5.07 (d, 1H), 5.00 (d, 1H), 2.19 (m, 2H), 1.39 (m, 2H), 1.30 (m, 2H), 1.04 (t, 2H), 0.10 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 139.4, 119.3, 118.8, 33.8, 32.0, 23.3, 15.4, 2.3.

(45) 3) Nucleophilic Addition Reaction of Functionalized Silyl Cyanide 1aaa to Aldehydes or Ketones (Table 3).

(46) ##STR00045##

(47) General procedure 3: a catalyst I, aldehyde or ketone 3a (1.0 mmol) and corresponding solvent (1 mL) were added into a dry Schlenk tube (25 mL). After being stirred at a corresponding temperature for 0.5 h, 1aaa (2.0 mmol) was added to the mixture. The reaction process was monitored by TLC analysis. After full consumption of raw material 3a, 4a as shown in Scheme (IIa) was obtained by conventional post-treatment followed by column chromatography, or by column chromatography directly.

(48) The specific experimental operations of the examples 38-115 are referred to general procedure 3. The specific reaction conditions and yield of each example are shown in Table 3.

(49) TABLE-US-00003 TABLE 3 Specific reaction conditions and yields of the examples 38-115. Ex- Product/ am- Catalyst I Temper- Yield (%)/ ple R.sup.2 R.sup.3 (mol %) Solvent ature Ee (%) 38 C.sub.6H.sub.5 H Li.sub.2CO.sub.3 (5) CH.sub.3CN 25 4aa/76/ 39 C.sub.6H.sub.5 Me Na.sub.2CO.sub.3 (5) DMF 25 4ab/88/ 40 C.sub.6H.sub.5 Et K.sub.2CO.sub.3 (5) DMSO 25 4ac/85/ 41 C.sub.6H.sub.5 i-Pr K.sub.2CO.sub.3 (25) CH.sub.3CN 50 4ad/90/ 42 C.sub.6H.sub.5 K.sub.2CO.sub.3 (25) CH.sub.3CN 50 4ae/92/ 43 C.sub.6H.sub.5 CO.sub.2Me KOAc (25) CH.sub.3CN 25 4af/95/ 44 C.sub.6H.sub.5 CO.sub.2Bn KOAc (25) CH.sub.3CN 25 4ag/79/ 45 C.sub.6H.sub.5 CONMe.sub.2 CsOAc (25) CH.sub.3CN 25 4ah/83/ 46 C.sub.6H.sub.5 CONEt.sub.2 LiOAc (25) THF 50 4ai/85/ 47 C.sub.6H.sub.5 Cy KOAc (50) CH.sub.3CN 50 4aj/88/ 48 C.sub.6H.sub.5 KOAc (25) DMF 25 4ak/79/ 49 C.sub.6H.sub.5 K.sub.2CO.sub.3 (15) THF 25 4al/77/ 50 C.sub.6H.sub.5 K.sub.2CO.sub.3 (15) CH.sub.3CN 80 4am/75/ 51 C.sub.6H.sub.5 0 K.sub.2CO.sub.3 (15) DMF 25 4an/69/ 52 4-ClC.sub.6H.sub.4 Me Et.sub.3N (5) THF 40 4ao/88/ 53 3-ClC.sub.6H.sub.4 Me toluene 50 4ap/85/ 54 4-FC.sub.6H.sub.4 Me Et.sub.3N (25) CH.sub.2Cl.sub.2 25 4ar/81/ 55 4-BrC.sub.6H.sub.4 Me (i-Pr).sub.2NEt (25) CH.sub.3CN 25 4as/81/ 56 3,4-Cl.sub.2C.sub.6H.sub.3 Et Et.sub.3N (25) CH.sub.2Cl.sub.2 25 4at/60/ 57 2,4,6-Me.sub.2C.sub.6H.sub.2 H DMAP (30) CH.sub.3CN 50 4au/90/ 58 4-NO.sub.2C.sub.6H.sub.4 Me DMF 25 4av/85/ 59 4-EtC.sub.6H.sub.4 Me K.sub.2CO.sub.3 (25) THF 0 4aw/85/ 60 4-MeC.sub.6H.sub.4 H K.sub.2CO.sub.3 (15) THF 0 4ax/82/ 61 Cy H Zn(OTf).sub.2 (0.1) CH.sub.3CN 25 4ay/85/ 62 Cy Me K.sub.2CO.sub.3 (1) DMF 50 4az/97/ 63 Me K.sub.2CO.sub.3 (5) THF 50 4aaa/80/ 64 H K.sub.2CO.sub.3 (2.5) toluene 10 4aab/92/ 65 H K.sub.3PO.sub.4 (2.5) CH.sub.2Cl.sub.2 10 4aac/90/ 66 H Na.sub.2PO.sub.4 (2.5) DMF 25 4aad/75/ 67 Me K.sub.2CO.sub.3 (10) THF 25 4aae/95/ 68 Me K.sub.2CO.sub.3 (10) CH.sub.3CN 25 4aaf/89/ 69 0 Me KI (10) DMF 25 4aag/91/ 70 Bn Me K.sub.2CO.sub.3 (5) THF 50 4aah/93/ 71 H K.sub.2CO.sub.3 (2.5) CH.sub.3CN 25 4aai/88/ 72 Me TiCl.sub.4 (0.5) toluene 0 4aaj/75/ 73 Me ZnI.sub.2 (0.5) CH.sub.3CN 25 4aak/84/ 74 Me TiCl.sub.4 (0.5) toluene 0 4aal/79/ 75 Me ZnI.sub.2 (0.5) CH.sub.3CN 25 4aam/85/ 76 Me KI (2.5) CH.sub.3CN 50 4aan/85/ 77 BnCH.sub.2 Me K.sub.2CO.sub.3 (2) CH.sub.3CN 50 4aao/95/ 78 Me K.sub.2CO.sub.3 (2.5) THF 25 4aap/85/ 79 Me K.sub.2CO.sub.3 (2.5) THF 25 4aaq/90/ 80 t-Bu H Zn(OTf).sub.2 (1) toluene 25 4aar/94/ 81 Et H Zn(OTf).sub.2 (1) toluene 25 4aas/80/ 82 i-Pr H Zn(OTf).sub.2 (1) toluene 25 4aat/87/ 83 C.sub.6H.sub.5 Me IC1 (10) (R.sup.4 = Me) CH.sub.2Cl.sub.2 0 4ab/88/85 84 C.sub.6H.sub.5 Et IC1 (10) (R.sup.4 = OEt) Et.sub.2O 0 4ac/85/83 85 C.sub.6H.sub.5 i-Pr IC1 (10) (R = OtBu) Et.sub.2O 0 4ad/90/75 86 C.sub.6H.sub.5 IC1 (20) (R = OEt) Et.sub.2O 0 4ae/92/60 87 C.sub.6H.sub.5 CO.sub.2Me IC4 (10) toluene 25 4af/95/77 88 C.sub.6H.sub.5 CONMe.sub.2 IC4 (20) toluene 25 4ah/83/80 89 C.sub.6H.sub.5 Cy IC6 (10) CH.sub.2Cl.sub.2 20 4aj/88/90 90 C.sub.6H.sub.5 0 IC1 (10) (R.sup.4 = OEt) CH.sub.2Cl.sub.2 25 4ak/79/95 91 C.sub.6H.sub.5 IC1 (10) (R.sup.4 = OEt) CH.sub.2Cl.sub.2 25 4al/77/86 92 C.sub.6H.sub.5 IC1 (10) (R.sup.4 = OEt) CH.sub.2Cl.sub.2 25 4an/69/80 93 4-ClC.sub.6H.sub.4 Me IC2 (10) (X.sup.1 = NTf.sub.2) toluene 40 4ao/88/94 94 3-ClC.sub.6H.sub.4 Me IC2 (10) (X.sup.1 = NTf.sub.2) toluene 40 4ap/85/92 95 2-ClC.sub.6H.sub.4 H IC2 (10) (X.sup.1 = OTf) THF 50 4aq/87/84 96 4-FC6H4 Me IC2 (10) (X.sup.1 = NTf.sub.2) CH.sub.2Cl.sub.2 40 4ar/81/90 97 4-BrC.sub.6H.sub.4 Me IC2 (10) (X.sup.1 = NTf.sub.2) toluene 40 4as/81/89 98 3,5-Cl.sub.2C.sub.6H.sub.3 H IC2 (10) (X.sup.1 = OTf) THF 40 4at/95/90 99 4-NO.sub.2C.sub.6H.sub.4 Me IC1 (10) (R.sup.4 = OEt) toluene 25 4av/85/97 100 4-MeC.sub.6H.sub.4 H IC2 (10) (X.sup.1 = OTf) CH.sub.2Cl.sub.2 25 4ax/82/88 101 Cy H IC2 (0.1) (X.sup.1 = OTf) THF 25 4ay/85/94 102 Cy Me IC1 (10) (R.sup.4 = OEt) Et.sub.2O 50 4az/97/95 103 Me IC3 (10) toluene 10 4aaa/80/93 104 H IC2 (0.1) (X.sup.1 = NTf.sub.2) toluene 50 4aab/92/84 106 Me IC1 (10) (R.sup.4 = OEt) Et.sub.2O 30 4aaf/89/94 107 Me IC1 (10) (R.sup.4 = OEt) Et.sub.2O 30 4aag/91/92 108 Bn Me IC1 (10) (R.sup.4 = OEt) Et.sub.2O 30 4aah/93/97 109 Me IC1 (10) (R.sup.4 = OEt) Et.sub.2O 10 4aaj/75/82 110 Me IC1 (10) (R.sup.4 = OEt) Et.sub.2O 30 4aak/84/84 111 Me IC1 (10) (R.sup.4 = OtBu) toluene 50 4aal/79/85 112 BnCH.sub.2 Me IC1 (10) (R.sup.4 = OEt) Et.sub.2O 30 4aao/95/96 113 t-Bu H IC2 (0.1) (X.sup.1 = OTf) THF 25 4aar/94/94 114 Et H IC2 (0.1) (X.sup.1 = OTf) THF 25 4aas/80/80 115 i-Pr H IC2 (0.1) (X.sup.1 = OTf) THF 25 4aat/87/89

(50) The characterizations of 4aa-4aat are as follows:

(51) ##STR00080##

(52) .sup.1H NMR (400 MHz, CDCl.sub.3): 7.38-7.36 (m, 5H), 5.51 (s, 1H), 3.67 (dd, 2H), 0.21 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 133.7, 128.8, 128.0, 127.5, 118.2, 34.6, 0.4;

(53) ##STR00081##

(54) .sup.1H NMR (400 MHz, CDCl.sub.3): 7.04-7.35 (m, 5H), 3.47 (dd, 2H), 1.87 (s, 3H), 0.22 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 136.7, 128.9, 128.0, 126.5, 119.2, 35.2, 30.9, 0.3;

(55) ##STR00082##

(56) .sup.1H NMR (400 MHz, CDCl.sub.3): 7.40-7.36 (m, 5H), 3.46 (dd, 2H), 1.87 (q, 2H), 0.87 (t, 2H), 0.22 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 146.7, 128.8, 126.0, 125.5, 119.0, 35.2, 32.9, 4.2, 0.4;

(57) ##STR00083##

(58) .sup.1H NMR (400 MHz, CDCl.sub.3): 7.49-7.32 (m, 5H), 2.72 (s, 2H), 2.66 (s, 1H), 0.90 (s, 6H), 0.21 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 140.84, 127.94, 127.68, 127.30, 121.50, 77.78, 41.09, 21.02, 16.79, 0.62;

(59) ##STR00084##

(60) .sup.1H NMR (400 MHz, CDCl.sub.3): 7.47-7.32 (m, 5H), 5.82 (dd, 1H), 5.07-5.02 (m, 2H), 3.47 (dd, 2H), 2.66 (dd, 2H), 0.21 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 137.86, 132.96, 128.69, 127.71, 127.36, 121.57, 118.52, 85.81, 44.11, 21.02, 0.62;

(61) ##STR00085##

(62) .sup.1H NMR (400 MHz, CDCl.sub.3): 7.49-7.38 (m, 10H), 5.34 (s, 2H), 2.74 (dd, 2H), 0.21 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 162.33, 133.85, 130.96, 128.17, 127.75, 119.13, 71.2, 62.33, 52.61, 21.02, 0.62;

(63) ##STR00086##

(64) .sup.1H NMR (400 MHz, CDCl.sub.3): 7.49-7.38 (m, 5H), 3.67 (s, 3H), 2.72 (dd, 2H), 0.21 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 161.67, 137.56, 133.85, 130.96, 129.01, 128.19, 128.17, 128.16, 127.75, 119.13, 71.2, 67.31, 62.61, 21.02, 0.62;

(65) ##STR00087##

(66) .sup.1H NMR (400 MHz, CDCl.sub.3): 7.42-7.34 (m, 5H), 3.44 (s, 6H), 2.59 (dd, 2H), 0.22 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 159.67, 131.22, 130.37, 129.41, 128.92, 111.80, 71.9, 64.00, 36.87, 21.02, 0.62;

(67) ##STR00088##

(68) .sup.1H NMR (400 MHz, CDCl.sub.3): 7.40-7.34 (m, 5H), 3.44 (s, 6H), 2.52 (dd, 2H), 1.08 (t, 6H), 0.21 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 163.66, 131.22, 130.37, 129.41, 128.92, 111.80, 71.9, 62.78, 43.22, 21.02, 13.15, 0.62;

(69) ##STR00089##

(70) .sup.1H NMR (400 MHz, CDCl.sub.3): 7.40-7.36 (m, 5H), 2.52 (dd, 2H), 1.78-1.43 (m, 11H), 0.22 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 140.01, 127.85, 127.54, 127.26, 121.44, 71.96, 44.87, 71.3, 27.52, 25.89, 21.02, 0.62;

(71) ##STR00090##

(72) .sup.1H NMR (400 MHz, CDCl.sub.3): 7.38-7.30 (m, 5H), 6.20 (dd, 1H), 5.04-4.98 (m, 2H), 2.56 (dd, 2H), 0.21 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 137.94, 134.89, 129.12, 128.58, 127.86, 121.48, 121.27, 71.2, 21.02, 0.62;

(73) ##STR00091##

(74) .sup.1H NMR (400 MHz, CDCl.sub.3): 7.40-7.30 (m, 5H), 6.10 (dd, 1H), 5.55 (m, 1H), 2.56 (dd, 2H), 2.05 (d, 2H), 0.21 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 134.42, 133.10, 130.59, 129.62, 128.11, 127.75, 121.45, 71.2, 21.02, 19.10, 0.62;

(75) ##STR00092##

(76) .sup.1H NMR (400 MHz, CDCl.sub.3): 7.43-7.35 (m, 5H), 6.10 (s, 1H), 2.56 (dd, 2H), 2.05 (s, 3H), 1.98 (s, 3H), 0.21 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 146.94, 134.04, 130.20, 127.69, 124.59, 121.43, 71.2, 25.84, 21.02, 19.65, 0.62;

(77) ##STR00093##

(78) .sup.1H NMR (400 MHz, CDCl.sub.3): 7.45-7.35 (m, 5H), 2.56 (dd, 2H), 1.88 (s, 3H), 0.21 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 132.03, 130.95, 128.11, 126.84, 104.69, 95.94, 78.15, 71.5, 21.02, 7.30, 0.62;

(79) ##STR00094##

(80) .sup.1H NMR (400 MHz, CDCl.sub.3): 7.50-7.38 (m, 5H), 2.83 (dd, 2H), 1.88 (s, 3H), 0.31 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 140.01, 135.12, 129.11, 126.12, 120.96, 71.55, 33.34, 29.57, 2.04, 2.12;

(81) ##STR00095##

(82) .sup.1H NMR (400 MHz, CDCl.sub.3): 7.54-7.35 (m, 5H), 2.85-2.80 (dd, 2H), 1.88 (s, 3H), 0.34 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 143.45, 135.01, 130.23, 129.31, 125.00, 122.86, 120.85, 71.48, 33.33, 29.54, 2.04, 2.12;

(83) ##STR00096##

(84) .sup.1H NMR (400 MHz, CDCl.sub.3): 7.58-7.36 (m, 5H), 2.87-2.79 (dd, 2H), 1.89 (s, 3H), 0.34 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 145.47, 136.01, 131.25, 129.71, 123.09, 121.86, 120.80, 71.48, 33.33, 29.54, 2.04, 2.12;

(85) ##STR00097##

(86) .sup.1H NMR (400 MHz, CDCl.sub.3): 7.52-7.38 (m, 5H), 2.81 (dd, 2H), 1.86 (s, 3H), 0.29 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 162.78, 136.32, 129.30, 123.36, 115.61, 72.39, 31.71, 21.02, 0.62;

(87) ##STR00098##

(88) .sup.1H NMR (400 MHz, CDCl.sub.3): 7.56-7.42 (m, 5H), 2.83 (dd, 2H), 1.86 (s, 3H), 0.32 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 140.54, 132.07, 126.40, 123.22, 120.89, 71.58, 33.30, 29.56, 2.04, 2.12;

(89) ##STR00099##

(90) .sup.1H NMR (400 MHz, CDCl.sub.3): 7.50 (s, 1H), 7.66-7.18 (m, 2H), 2.86-2.80 (dd, 2H), 1.87 (q, 2H), 0.90 (t, 3H), 0.30 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 135.27, 134.72, 131.86, 127.12 (d, J=8.0 Hz), 126.86, 121.95, 86.43, 38.52, 21.02, 7.77, 0.62.

(91) ##STR00100##

(92) .sup.1H NMR (400 MHz, CDCl.sub.3): 6.84 (s, 2H), 5.50 (s, 1H), 2.63 (dd, 2H), 2.38 (s, 6H), 2.30 (s, 3H), 0.21 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 140.28, 140.06, 129.81, 126.37, 118.63, 57.44, 28.43, 21.83, 20.50, 1.86.

(93) ##STR00101##

(94) .sup.1H NMR (400 MHz, CDCl.sub.3): 8.30-7.75 (m, 4H), 2.90 (dd, 1H), 1.92 (s, 3H), 0.38 (s, 3H), 0.36 (s, 3H); .sup.13C NMR (100 MHz, CDCl.sub.3): 148.30, 148.16, 125.78, 124.19, 120.38, 71.32, 33.32, 29.42, 1.95, 2.07;

(95) ##STR00102##

(96) .sup.1H NMR (400 MHz, CDCl.sub.3): 7.31-7.05 (dd, 4H), 2.90 (dd, 1H), 2.60 (q, 3H), 1.82 (s, 3H), 1.25 (t, 3H), 0.30 (s, 3H); .sup.13C NMR (100 MHz, CDCl.sub.3): 143.43, 137.34, 127.08, 123.79, 123.36, 72.39, 31.71, 27.82, 21.02, 13.19, 1.62.

(97) ##STR00103##

(98) .sup.1H NMR (400 MHz, CDCl.sub.3): 7.20-7.00 (dd, 4H), 2.90 (dd, 1H), 2.30 (s, 3H), 1.82 (s, 3H), 0.30 (s, 3H); .sup.13C NMR (100 MHz, CDCl.sub.3): 138.02, 137.60, 128.16, 127.40, 123.36, 72.39, 31.71, 21.09 (d, J=15.7 Hz), 1.62.

(99) ##STR00104##

(100) .sup.1H NMR (400 MHz, CDCl.sub.3): 4.20 (d, 1H), 2.97 (dd, 2H), 1.90 (m, 1H), 1.53-1.27 (m, 10H), 0.22 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 118.88, 65.71, 39.88, 28.93, 28.43, 25.92, 25.57, 1.86;

(101) ##STR00105##

(102) .sup.1H NMR (400 MHz, CDCl.sub.3): 2.87 (dd, 2H), 1.96 (d, 1H), 1.84-1.81 (m, 3H), 1.69 (d, J=10.8 Hz, 1H), 1.56 (s, 3H), 1.52-1.48 (m, 1H), 1.26-1.07 (m, 5H), 0.38 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 121.55, 73.61, 48.41, 29.91, 27.30, 27.06, 26.27, 26.00, 25.93, 1.78, 1.90;

(103) ##STR00106##

(104) .sup.1H NMR (400 MHz, CDCl.sub.3): 8.18 (s, 1H), 8.05-7.95 (m, 2H), 7.54-7.42 (m, 4H), 5.48 (s, 1H), 2.85 (dd, 1H), 0.31 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 138.44, 133.41, 132.87, 129.10, 128.49, 127.78, 127.05, 126.96, 123.90, 122.16, 121.35, 72.34, 33.28, 29.72, 2.06, 2.13;

(105) ##STR00107##

(106) .sup.1H NMR (400 MHz, CDCl.sub.3): 8.05 (s, 1H), 7.91-7.85 (m, 3H), 7.60 (m, 1H), 7.55-7.53 (m, 2H), 2.80 (dd, 1H), 1.97 (s, 3H), 0.31 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 136.00, 132.47, 130.51, 128.89, 128.45, 128.25, 127.61, 127.25, 127.01, 122.81, 118.37, 60.96, 28.43, 1.96;

(107) ##STR00108##

(108) .sup.1H NMR (400 MHz, CDCl.sub.3): 8.05-7.95 (m, 2H), 7.51-7.43 (m, 4H), 5.50 (s, 1H), 2.80 (dd, 1H), 2.45 (s, 3H), 0.31 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 136.72, 134.82, 134.15, 133.63, 129.61, 128.29, 127.93, 127.65, 121.64, 119.02, 117.08, 61.42, 28.43, 21.71, 1.86;

(109) ##STR00109##

(110) .sup.1H NMR (400 MHz, CDCl.sub.3): 8.08 (s, 1H), 7.99-7.93 (m, 2H), 7.38 (s, 1H), 7.05-6.99 (m, 2H), 2.83 (dd, 2H), 2.46 (s, 3H), 1.87 (s, 3H), 0.21 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 137.13, 134.15, 133.36, 133.04, 128.78, 128.22, 126.76, 126.20, 126.02, 122.72, 117.76, 60.00, 28.43, 20.35, 1.86;

(111) ##STR00110##

(112) .sup.1H NMR (400 MHz, CDCl.sub.3): 8.05 (s, 1H), 7.91-7.85 (m, 3H), 7.60 (m, 1H), 7.55-7.53 (m, 2H), 2.80 (dd, 1H), 1.97 (s, 3H), 0.31 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 135.61, 134.64, 133.51, 131.21, 130.41, 127.93, 127.71, 127.47, 126.98, 124.99, 124.59, 70.29, 30.63, 21.71, 21.02, 0.62;

(113) ##STR00111##

(114) .sup.1H NMR (400 MHz, CDCl.sub.3): 7.18 (s, 1H), 6.82 (dd, 2H), 4.48-4.34 (m, 4H), 2.85 (dd, 1H), 1.85 (s, 3H), 0.31 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 149.53, 143.03, 126.95, 123.36, 121.49, 117.25, 110.05, 71.70, 61.57, 31.71, 21.02, 1.62;

(115) ##STR00112##

(116) .sup.1H NMR (400 MHz, CDCl.sub.3): 6.99 (d, 2H), 6.87 (s, 1H), 5.97 (s, 2H), 2.72 (s, 2H), 2.14 (s, 3H), 0.21 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 151.58, 147.84, 132.17, 123.36, 123.13, 111.80, 104.82, 101.95, 71.70, 31.71, 21.02, 2.02;

(117) ##STR00113##

(118) .sup.1H NMR (400 MHz, CDCl.sub.3): 7.40-7.29 (m, 5H), 4.21 (s, 1H), 3.30 (dd, 2H), 2.98 (dd, 2H), 1.70 (m, 2H), 0.23 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 136.86, 131.37, 128.99, 126.52, 108.38, 71.73, 43.63, 28.27, 21.02, 0.62;

(119) ##STR00114##

(120) .sup.1H NMR (400 MHz, CDCl.sub.3): 7.17 (d, 1H), 5.89 (d, 1H), 5.54 (s, 1H), 5.46 (s, 1H), 3.89 (s, 3H), 2.89 (dd, 2H), 0.27 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 162.06, 133.50, 123.31, 113.36, 112.44, 107.34, 58.24, 52.08, 28.43, 1.76;

(121) ##STR00115##

(122) .sup.1H NMR (400 MHz, CDCl.sub.3): 7.67 (d, 1H), 6.47-6.39 (m, 2H), 2.89 (dd, 2H), 1.88 (s, 3H), 0.23 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 158.66, 142.80, 118.78, 112.07, 105.96, 74.67, 29.37, 21.02, 1.62;

(123) ##STR00116##

(124) .sup.1H NMR (400 MHz, CDCl.sub.3): 6.27-6.03 (m, 2H), 2.83 (dd, 2H), 2.30 (dd, 3H), 1.86 (s, 3H), 0.23 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 158.49, 155.72, 118.78, 109.82, 108.25, 75.26, 29.37, 21.02, 14.79, 1.66;

(125) ##STR00117##

(126) .sup.1H NMR (400 MHz, CDCl.sub.3): 6.57-6.53 (m, 2H), 2.84 (dd, 2H), 2.36 (s, 3H), 1.88 (s, 3H), 0.21 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 142.28, 142.06, 126.40, 120.85, 114.09, 79.52, 30.74, 21.02, 17.13, 1.62;

(127) ##STR00118##

(128) .sup.1H NMR (400 MHz, CDCl.sub.3): 5.57-5.53 (m, 2H), 5.03 (s, 1H), 2.54 (dd, 2H), 2.16 (s, 3H), 1.80 (s, 3H), 0.19 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 139.22, 132.45, 123.36, 106.96, 105.88, 70.68, 30.20, 21.02, 13.43, 1.52;

(129) ##STR00119##

(130) .sup.1H NMR (400 MHz, CDCl.sub.3): 7.95-7.53 (m, 3H), 2.73 (s, 3H), 2.84 (dd, 2H), 2.56 (s, 3H), 1.87 (s, 3H), 0.19 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 160.63, 156.83, 140.70, 124.71, 123.91, 119.14, 69.32, 29.74, 24.29, 21.02, 0.62;

(131) ##STR00120##

(132) .sup.1H NMR (400 MHz, CDCl.sub.3): 7.32-7.28 (m, 2H), 7.23-7.19 (m, 3H), 2.90-2.78 (m, 4H), 2.08-2.04 (m, 2H), 1.66 (s, 3H), 0.40 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 140.51, 128.67, 128.43, 126.35, 121.59, 69.92, 45.04, 30.74, 29.81, 29.02, 1.73, 1.82;

(133) ##STR00121##

(134) .sup.1H NMR (400 MHz, CDCl.sub.3): 8.39 (s, 1H), 7.85-7.53 (dd, 2H), 2.84 (dd, 2H), 2.33 (s, 3H), 1.88 (s, 3H), 0.21 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 156.16, 148.39, 132.96, 131.39, 123.91, 117.27, 69.17, 29.74, 21.02, 18.43, 1.62;

(135) ##STR00122##

(136) .sup.1H NMR (400 MHz, CDCl.sub.3): 8.49 (d, 1H), 7.87 (s, 1H), 7.53 (d, 1H), 2.94 (dd, 2H), 2.36 (s, 3H), 1.87 (s, 3H), 0.22 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 157.81, 149.77, 147.81, 125.60, 123.91, 118.49, 68.85, 29.74, 21.23, 21.02, 1.72;

(137) ##STR00123##

(138) .sup.1H NMR (400 MHz, CDCl.sub.3): 4.26 (s, 1H), 2.97 (dd, 2H), 0.94 (s, 9H), 0.23 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 121.84, 73.83, 34.39, 28.43, 27.08, 1.86;

(139) ##STR00124##

(140) .sup.1H NMR (400 MHz, CDCl.sub.3): 4.22 (s, 1H), 2.98 (dd, 2H), 1.85 (q, 2H), 0.90 (t, 3H), 0.22 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 119.12, 64.40, 28.43, 26.00, 10.41, 1.86;

(141) ##STR00125##

(142) .sup.1H NMR (400 MHz, CDCl.sub.3): 4.21 (d, 1H), 2.98 (dd, 2H), 1.90 (m, 2H), 0.90 (d, 6H), 0.22 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 118.35, 69.93, 37.79, 28.43, 18.42, 1.86;

(143) 4) Nucleophilic Addition Reaction of Functionalized Silyl Cyanide 1aaa with Imines (Table 4).

(144) ##STR00126##

(145) General procedure 4: a catalyst I (0.1 mmol), imine 3b (1.0 mmol) and a corresponding solvent (1 mL) were added into a dry Schlenk tube (25 mL). The mixture was added with 1aaa (2.0 mmol) after being stirred at the corresponding temperature for 0.5 h. The progress of the reaction was monitored by TLC analysis. After full consumption of the raw material 3b, 4b as shown in Scheme (IIb) was obtained by conventional post-treatment followed by column chromatography, or by column chromatography directly.

(146) The specific experimental operations of the examples 116-159 are referred to general procedure 4. The specific reaction conditions and yields of each example are shown in Table 4.

(147) TABLE-US-00004 TABLE 4 Specific reaction conditions and yields of the examples 116-159. Product/ Ex- Temper- Yield am- Catalyst I ature (%)/ ple R.sup.2 R.sup.3 PG (ml %) Solvent ( C.) Ee (%) 116 C.sub.6H.sub.5 H Bn DMAP (25) CH.sub.3CN 25 4ba/79/ 117 C.sub.6H.sub.5 H CBz DMAP (2.5) toluene 25 4bb/86/ 118 C.sub.6H.sub.5 H Ts DMAP (2.5) CH.sub.2Cl.sub.2 25 4bc/88/ 119 C.sub.6H.sub.5 H Boc DMAP (2.5) CH.sub.2Cl.sub.2 25 4bd/93/ 120 C.sub.6H.sub.5 H PMP DMAP (15) CH.sub.3CN 25 4be/82/ 121 C.sub.6H.sub.5 H P(O)Ph.sub.2 DMAP (5) toluene 25 4bf/90/ 122 C.sub.6H.sub.5 H PMP DMAP (15) CH.sub.2Cl.sub.2 25 4bg/89/ 123 C.sub.6H.sub.5 CONMe.sub.2 PMP DMAP (50) CH.sub.2Cl.sub.2 25 4bh/86/ 124 C.sub.6H.sub.5 CONEt.sub.2 PMP DMAP (50) THF 50 4bi/88/ 125 C.sub.6H.sub.5 Me PMP KOAc (15) CH.sub.3CN 50 4bj/85/ 126 C.sub.6H.sub.5 CO.sub.2Me PMP KOAc (25) toluene 25 4bk/89/ 127 C.sub.6H.sub.5 CO.sub.2Et PMP K.sub.2CO.sub.3 (25) CH.sub.2Cl.sub.2 25 4bl/87/ 128 C.sub.6H.sub.5 CO.sub.2tBu PMP K.sub.2CO.sub.3 (25) CH.sub.2Cl.sub.2 50 4bm/78/ 129 C.sub.6H.sub.5 CO.sub.2Bn PMP K.sub.2CO.sub.3 (25) CH.sub.3CN 25 4bn/89/ 130 4-ClC.sub.6H.sub.4 H Ts Et.sub.3N (15) THF 40 4bo/87/ 131 3-ClC.sub.6H.sub.4 H Ts (i-Pr).sub.2NEt (25) toluene 50 4bp/83/ 132 2-ClC.sub.6H.sub.4 H Ts Et.sub.3N (15) CH.sub.2Cl.sub.2 55 4bq/87/ 133 4-FC.sub.6H.sub.4 H Ts Et.sub.3N (15) CH.sub.2Cl.sub.2 25 4br/85/ 134 4-BrC.sub.6H.sub.4 H Ts (i-Pr).sub.2NEt (25) CH.sub.3CN 25 4bs/82/ 135 H Ts DABCO (5) toluene 50 4bt/95/ 136 0 H Ts DMAP (5) CH.sub.2Cl.sub.2 25 4bu/85/ 137 H Ts DMAP (5) CH.sub.2Cl.sub.2 50 4bv/80/ 138 H Ts DMAP (5) CH.sub.3CN 25 4bw/89/ 139 Bn H PMP ZnI.sub.2 (0.5) CH.sub.2Cl.sub.2 0 4bx/82/ 140 BnCH.sub.2 H PMP TiCl.sub.4 (2.5) CH.sub.2Cl.sub.2 0 4by/87/ 141 Cy H PMP Et.sub.3N (5) CH.sub.2Cl.sub.2 0 4bz/92/ 142 C.sub.6H.sub.5 H Bn IC3 (20) CH.sub.3CN 20 4ba/83/75 143 C.sub.6H.sub.5 H CBz IC3 (5) toluene 20 4bb/96/90 144 C.sub.6H.sub.5 H Ts IC3 (10) CH.sub.2Cl.sub.2 20 4bc/89/94 145 C.sub.6H.sub.5 H Boc IC3 (5) CH.sub.2Cl.sub.2 20 4bd/93/93 146 C.sub.6H.sub.5 H PMP IC3 (10) CH.sub.2Cl.sub.2 20 4be/86/87 147 C.sub.6H.sub.5 H P(O)Ph.sub.2 IC3 (20) CH.sub.2Cl.sub.2 20 4bf/80/88 148 4-ClC.sub.6H.sub.4 H Ts IC3 (10) CH.sub.2Cl.sub.2 20 4bo/92/93 149 3-ClC.sub.6H.sub.4 H Ts IC3 (10) CH.sub.2Cl.sub.2 20 4bp/95/84 150 2-ClC.sub.6H.sub.4 H Ts IC3 (10) CH.sub.2Cl.sub.2 20 4bq/87/82 151 4-FC.sub.6H.sub.4 H Ts IC3 (10) CH.sub.2Cl.sub.2 20 4br/84/94 152 4-BrC.sub.6H.sub.4 H Ts IC3 (10) CH.sub.2Cl.sub.2 20 4bs/86/93 153 H Ts IC3 (10) CH.sub.2Cl.sub.2 20 4bt/94/95 154 H Ts IC3 (10) CH.sub.2Cl.sub.2 20 4bu/95/82 155 H Ts IC3 (10) CH.sub.2Cl.sub.2 20 4bv/90/90 156 H Ts IC3 (10) CH.sub.2Cl.sub.2 20 4bw/89/91 157 Bn H PMP IC3 (20) CH.sub.2Cl.sub.2 20 4bx/80/68 158 BnCH.sub.2 H PMP IC3 (20) CH.sub.2Cl.sub.2 20 4by/90/75 159 Cy H PMP IC3 (20) CH.sub.2Cl.sub.2 20 4bz/92/90

(148) Products 4ba-4bz are known compounds. The characterizations of the products 4ba, 4be are consistent with the literature (Chem. Comm. 2009, 34, 5180); the characterizations of the products 4bb, 4bd are consistent with the literature (Org. Lett. 2012, 14, 882); the characterizations of the products 4bc, 4bj, 4bo, 4br, 4bt, 4bu, 4bw, 4bx, 4bz are consistent with the literature (Angew. Chem. Int. Ed. 2007, 46, 8468); the characterization of the product 4bf is consistent with the literature (J. Am. Chem. Soc. 2009, 131, 15118); the characterizations of the products 4bg, 4by are consistent with the literature (Tetrahedron Lett. 2012, 53, 1075); the characterizations of the products 4bh, 4bi, 4bk, 4bl, 4bm, 4bn are consistent with the literature (Angew. Chem. Int. Ed. 2015, 54, 13655); the characterizations of the products 4 bp, 4bv are consistent with the literature (Tetrahedron Lett. 2004, 45, 9565); and the characterizations of the products 4bq, 4bs, 4bx are consistent with the literature (Tetrahedron Lett. 2014, 55, 232).

(149) 5) Addition Reaction of the Functionalized Silyl Cyanide 1aaa with an Electron-Deficient Olefin (Table 5).

(150) ##STR00137##

(151) General procedure 5: the catalyst I (0.1 mmol), an electron-deficient olefin 3c (1.0 mmol) and a corresponding solvent (1 mL) were added into a dry Schlenk tube (25 mL). The mixture was added with the 1aaa (2.0 mmol) after being stirred at a corresponding temperature for 0.5 h. The progress of the reaction was monitored by TLC analysis. After the consumption of the raw material 3c was complete, 4c as shown in Scheme (IIc) was obtained by conventional post-treatment followed by column chromatography, or by column chromatography directly.

(152) The specific experimental operations of the examples 160-182 are referred to general procedure 5. The specific reaction conditions and yield of each example are shown in Table 5.

(153) TABLE-US-00005 TABLE 5 Specific reaction conditions and yields of the examples 160-182. Product/ Yield Catalyst I Temperature (%)/Ee Example R.sup.2 R.sup.3 EWG (ml %) Solvent ( C.) (%) 160 C.sub.6H.sub.5 H NO.sub.2 DMAP CH.sub.3CN 25 4ca/79/ (25) 161 C.sub.6H.sub.5 H CO.sub.2Me DMAP toluene 25 4cb/86/ (2.5) 162 C.sub.6H.sub.5 H CONMe.sub.2 DMAP CH.sub.3CN 25 4cc/82/ (15) 163 4-ClC.sub.6H.sub.4 H NO.sub.2 Et.sub.3N (15) THF 40 4cd/87/ 164 3-NO.sub.2C.sub.6H.sub.4 H NO.sub.2 (i-Pr).sub.2NEt toluene 50 4ce/83/ (25) 165 2-ClC.sub.6H.sub.4 H NO.sub.2 Et.sub.3N (15) CH.sub.2Cl.sub.2 55 4cf/87/ 166 4-NO.sub.2C.sub.6H.sub.4 H NO.sub.2 Et.sub.3N (15) THF 40 4cg/87/ 167 4-OMeC.sub.6H.sub.4 H NO.sub.2 Et.sub.3N (15) THF 40 4ch/87/ 168 4-FC.sub.6H.sub.4 H NO.sub.2 Et.sub.3N (15) THF 40 4ci/89/ 169 Cy H NO.sub.2 Et.sub.3N (5) CH.sub.2Cl.sub.2 0 4cj/92/ 170 Ph Me NO.sub.2 Et.sub.3N (25) CH.sub.2Cl.sub.2 70 4ck/86/ 171 Ph CF.sub.3 NO.sub.2 Et.sub.3N (25) CH.sub.2Cl.sub.2 30 4cl/80/ 172 C.sub.6H.sub.5 H NO.sub.2 IC1 toluene 20 4ca/79/85 (R.sup.4 = OEt) 173 C.sub.6H.sub.5 H CO.sub.2Me IC1 toluene 20 4cb/86/80 (R.sup.4 = OEt) 174 C.sub.6H.sub.5 H CONMe.sub.2 IC1 toluene 20 4cc/82/68 (R.sup.4 = OEt) 175 4-ClC.sub.6H.sub.4 H NO.sub.2 IC1 THF 20 4cd/87/88 (R.sup.4 = OEt) 176 3-NO.sub.2C.sub.6H.sub.4 H NO.sub.2 IC1 toluene 20 4ce/83/87 (R.sup.4 = OEt) 177 2-ClC.sub.6H.sub.4 H NO.sub.2 IC1 CH.sub.2Cl.sub.2 20 4cf/87/80 (R.sup.4 = OEt) 178 4-NO.sub.2C.sub.6H.sub.4 H NO.sub.2 IC1 THF 20 4cg/87/86 (R.sup.4 = OEt) 179 4-OMeC.sub.6H.sub.4 H NO.sub.2 IC1 THF 20 4ch/87/88 (R.sup.4 = OEt) 180 Cy H NO.sub.2 IC1 CH.sub.2Cl.sub.2 20 4cj/92/87 (R.sup.4 = OEt) 181 Ph Me NO.sub.2 IC1 CH.sub.2Cl.sub.2 20 4ck/90/70 (R.sup.4 = OEt) 182 Ph CF.sub.3 NO.sub.2 IC1 CH.sub.2Cl.sub.2 20 4cl/80/85 (R.sup.4 = OEt)

(154) Products 4ca-4c1 are known compounds. The characterizations of the compounds 4ca, 4cd-h are consistent with the literature (Tetrahedron Lett. 2009, 50, 640); the characterization of the compound 4cb is consistent with the literature (Org. Biomol. Chem. 2010, 8, 533); the characterization of the compound 4cj is consistent with the literature (Org. Lett. 2008, 10, 4141); the characterization of the compound 4ck is consistent with the literature (Chem. Eur. 12015, 21, 1280); and the characterization of the compound 4c1 is consistent with the literature (RSC Adv. 2016, 6, 29977).

(155) 6) Nucleophilic Addition Reaction of Different Functionalized Silyl Cyanide 1a with Ketone 3Aao (Table 6).

(156) ##STR00138##

(157) General procedure 6: a catalyst IC1 (R.sup.4=OEt) (0.05 mol), ketone 3aao (1 mmol) and Et.sub.2O (1 mL) were added into a dry Schlenk tube (25 mL). The mixture was added with 1a after being stirred at a corresponding temperature for 0.5 h. The progress of the reaction was monitored by TLC analysis. After the consumption of the raw material 3aao was complete, 4d as shown in Scheme (IId) was obtained by conventional post-treatment followed by column chromatography, or by column chromatography directly, wherein, the compound 4d is in R or S configuration.

(158) The specific experimental operations of the examples 183-199 are referred to general procedure 6. The specific reaction conditions and yield of each example are shown in Table 6.

(159) TABLE-US-00006 TABLE 6 Specific reaction conditions and yields of the examples 183-199. Temperature Product/ Example 1a (mmol) ( C.) Yield (%)/Ee (%) 183 1aab (1.0) 30 4da/76/95 184 1aab (1.2) 30 4da/89/95 185 1aab (1.5) 30 4da/95/95 186 1aab (1.75) 30 4da/96/95 187 1aab (2.0) 30 4da/96/95 188 1aab (2.5) 30 4da/97/93 189 1aab (3.0) 30 4da/98/90 190 1aba (1.5) 40 4db/96/93 191 1aea (1.5) 0 4dc/79/85 192 1aeb (1.5) 0 4dd/87/88 193 1abc (1.5) 10 4de/89/94 194 1aec (1.5) 10 4df/91/87 195 1abd (1.5) 20 4dg/96/96 196 1abc (1.5) 40 4dh/89/95 197 1aca (1.5) 20 4di/88/90 198 1ada (1.5) 10 4dj/92/90 199 1adb (1.5) 20 4dk/94/94

(160) The characterizations of 4da-4dk are as follows:

(161) ##STR00139##

(162) .sup.1H NMR (400 MHz, CDCl.sub.3): 7.42-7.29 (m, 2H), 7.29-7.19 (m, 3H), 2.60-2.48 (m, 4H), 2.08-2.04 (m, 2H), 1.67 (s, 3H), 0.40 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 140.55, 128.17, 128.33, 126.45, 121.79, 69.82, 45.44, 30.84, 30.91, 29.12, 1.75, 1.86;

(163) ##STR00140##

(164) .sup.1H NMR (400 MHz, CDCl.sub.3): 7.41-7.30 (m, 2H), 7.26-7.17 (m, 3H), 5.30 (dd, 1H), 5.22-5.17 (m, 2H), 2.55-2.48 (m, 2H), 2.08-2.04 (m, 2H), 1.68 (s, 3H), 0.42 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 143.84, 140.87, 128.91, 128.43, 128.11, 126.57, 119.43, 69.88, 40.92, 33.90, 27.60, 1.78, 1.89;

(165) ##STR00141##

(166) .sup.1H NMR (400 MHz, CDCl.sub.3): 7.47-7.32 (m, 2H), 7.26-7.17 (m, 3H), 2.81 (s, 1H), 2.55-2.48 (m, 2H), 2.08-2.04 (m, 2H), 1.68 (s, 3H), 0.42 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 140.87, 128.91, 128.43, 126.57, 119.43, 118.74, 70.41, 51.51, 40.92, 33.90, 27.60, 1.78, 1.89;

(167) ##STR00142##

(168) .sup.1H NMR (400 MHz, CDCl.sub.3): 7.47-7.32 (m, 2H), 7.26-7.17 (m, 3H), 2.83 (s, 1H), 2.56-2.47 (m, 2H), 2.08-2.04 (m, 4H), 1.70 (s, 3H), 1.25 (t, 2H), 0.42 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 140.87, 128.91, 128.43, 126.57, 119.43, 84.72, 68.96, 64.57, 40.92, 33.90, 27.60, 18.16, 12.42, 1.78, 1.89;

(169) ##STR00143##

(170) .sup.1H NMR (400 MHz, CDCl.sub.3): 7.49-7.37 (m, 2H), 7.28-7.19 (m, 3H), 5.30 (t, 1H), 2.54 (t, 2H), 2.09 (t, 2H), 2.00 (d, 2H), 1.69 (s, 3H), 1.59 (s, 3H), 1.44 (s, 3H), 0.43 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 140.87, 128.91, 128.43, 127.89, 126.57, 119.83, 119.43, 68.96, 40.92, 33.90, 27.60, 25.15, 18.07, 14.78, 1.77, 1.88;

(171) ##STR00144##

(172) .sup.1H NMR (400 MHz, CDCl.sub.3): 7.55-7.40 (m, 2H), 7.26-7.17 (m, 3H), 2.54 (t, 2H), 2.09 (t, 2H), 1.80 (s, 3H), 1.69 (s, 3H), 0.42 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 140.87, 128.91, 128.43, 126.57, 119.43, 103.01, 79.50, 70.41, 40.92, 33.90, 27.60, 7.11, 1.78, 1.89;

(173) ##STR00145##

(174) .sup.1H NMR (400 MHz, CDCl.sub.3): 7.41-7.30 (m, 2H), 7.26-7.17 (m, 3H), 5.97-5.80 (m, 1H), 5.17-5.19 (m, 2H), 2.57 (t, 2H), 2.49-2.15 (m, 4H), 1.81 (m, 2H), 1.39-1.25 (m, 4H), 1.15-1.08 (m, 2H), 0.43 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 140.87, 138.80, 128.91, 128.43, 126.57, 119.43, 114.45, 68.96, 40.92, 35.17, 33.90, 29.94, 27.60, 23.57, 15.78, 1.77, 1.88;

(175) ##STR00146##

(176) .sup.1H NMR (400 MHz, CDCl.sub.3): 7.41-7.30 (m, 2H), 7.26-7.17 (m, 3H), 5.70 (dd, 1H), 5.12-5.07 (m, 2H), 2.55-2.48 (m, 2H), 2.08-2.04 (m, 4H), 1.69 (s, 3H), 0.43 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 140.87, 135.46, 128.91, 128.43, 126.57, 119.43, 110.94, 68.96, 40.92, 33.90, 27.60, 23.11, 1.77, 1.88;

(177) ##STR00147##

(178) .sup.1H NMR (400 MHz, CDCl.sub.3): 7.43-7.33 (m, 2H), 7.29-7.18 (m, 3H), 5.70 (s, 1H), 2.58-2.48 (m, 2H), 2.08-2.04 (m, 2H), 1.75 (s, 3H), 0.49 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 140.87, 128.91, 128.43, 126.57, 119.43, 69.17, 40.92, 33.90, 27.86, 17.56, 1.77, 1.88;

(179) ##STR00148##

(180) .sup.1H NMR (400 MHz, CDCl.sub.3): 7.42-7.29 (m, 2H), 7.29-7.19 (m, 3H), 5.30-5.17 (m, 1H), 2.54 (t, 4H), 2.08 (t, 2H), 1.69 (s, 3H), 1.48-1.40 (m, 2H), 0.43 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 140.87, 128.91, 128.43, 126.57, 119.43, 68.96, 50.36, 40.92, 33.90, 27.60, 1.75, 1.86;

(181) ##STR00149##

(182) .sup.1H NMR (400 MHz, CDCl.sub.3): 7.43-7.30 (m, 2H), 7.24-7.15 (m, 3H), 5.40 (t, 1H), 2.55 (t, 4H), 2.07 (t, 2H), 1.69 (s, 3H), 1.58 (d, 2H), 0.44 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 140.87, 128.91, 128.43, 126.57, 119.43, 92.42, 69.76, 68.96, 40.92, 33.90, 27.60, 1.75, 1.86.

(183) 7) Tandem Nucleophilic Addition Reaction/Functional Group Transfer Reaction of the Functionalized Silyl Cyanide 1aa (Table 7)

(184) ##STR00150##

(185) General procedure 7: the catalyst I, the raw material of 3a (1.0 mmol) and a corresponding solvent (1 mL) were added into a dry Schlenk tube (25 mL). The mixture was added with 1aa (1.5 mmol) after being stirred at a T.sub.1 temperature for 0.5 h. The progress of the reaction was monitored by TLC analysis. After the consumption of the raw material 3a was complete, the crude product 4a was obtained by filtering the reaction mixture by 5 cm silica gel column, eluting with Et.sub.2O, and removing solvent under reduced pressure. The crude product 4a was transferred to a dry Schlenk tube (25 mL) and dissolved with anhydrous THF (4.0 mL). The resulting solution was stirred at a T.sub.2 temperature for 0.5 h, and base I was added dropwise slowly. The process of the reaction was monitored by TLC analysis. After the consumption of 4a was complete, the reaction was quenched by 5 mL acid I (4 M). The resulting mixture was extracted three times with EtOAc. Product 5 as shown in Scheme (III) was obtained by rotary evaporation of the solvent and column chromatography.

(186) The specific experimental operations of the examples 200-241 are referred to general procedure 7. The specific reaction conditions and yield of each example are shown in Table 7.

(187) TABLE-US-00007 TABLE 7 Specific reaction conditions and yields of the examples 200-241. Ex- Catalyst Product/ am- I T.sub.1 Base I (eq) Yield (%)/ ple R.sup.2/R.sup.3/Z (mol %) Solvent ( C.) T.sub.2 ( C.) Acid I Ee (%) 200 BnCH.sub.2/Me/Cl Na.sub.2CO.sub.3 (5) MeCN 25 LDA Hydrochloric 5a/68/ (1.2) 30 acid 201 BnCH.sub.2/Me/Cl Na.sub.2CO.sub.3 (5) MeCN 25 LDA Hydrochloric 5a/80/ (1.5) 30 acid 202 BnCH.sub.2/Me/Cl Na.sub.2CO.sub.3 (5) MeCN 25 LDA Hydrochloric 5a/78/ (2.0) 30 acid 203 BnCH.sub.2/Me/Cl Na.sub.2CO.sub.3 (5) MeCN 25 LDA Hydrochloric 5a/75/ (3.0) 30 acid 204 BnCH.sub.2/Me/Cl Na.sub.2CO.sub.3 (5) MeCN 25 LDA Hydrochloric 5a/65/ (1.5) 30 acid 205 BnCH.sub.2/Me/Cl Na.sub.2CO.sub.3 (5) MeCN 25 LDA Sulfuric 5a/78/ (1.5) 30 acid 206 BnCH.sub.2/Me/Cl Na.sub.2CO.sub.3 (5) MeCN 25 NaHMDS Hydrochloric 5a/38/ (1.5) 30 acid 207 BnCH.sub.2/Me/Cl Na.sub.2CO.sub.3 (5) MeCN 25 LDA Hydrochloric 5a/66/ (1.5) 78 acid 208 BnCH.sub.2/Me/Cl Na.sub.2CO.sub.3 (5) MeCN 25 LDA Hydrochloric 5a/75/ (1.5) 50 acid 209 BnCH.sub.2/Me/Cl Na.sub.2CO.sub.3 (5) MeCN 25 LDA Hydrochloric 5a/68 (1.5) 0 acid 210 BnCH.sub.2/Me/Cl Na.sub.2CO.sub.3 (5) MeCN 25 LDA Hydrochloric 5a/39/ (1.5) 30 acid 211 BnCH.sub.2/Et/Cl K.sub.2CO.sub.3 (5) MeCN 25 LDA Hydrochloric 5b/78/ (1.5) 30 acid 212 BnCH.sub.2/i-Pr/Cl K.sub.2CO.sub.3 (5) MeCN 50 LDA Hydrochloric 5c/74/ (1.5) 30 acid 213 KOAc (25) MeCN 25 LDA (1.5) 30 Hydrochloric acid 5d/68/ 214 K.sub.2CO.sub.3 (15) THF 25 LDA (1.5) 30 Hydrochloric acid 5e/57/ 215 4-ClC.sub.6H.sub.4/Me/Cl Et.sub.3N (5) THF 40 LDA Hydrochloric 5f/64/ (1.5) 30 acid 216 4-MeC.sub.6H.sub.4/Me/Cl K.sub.2CO.sub.3 (25) THF 0 LDA Hydrochloric 5g/75/ (1.5) 30 acid 217 DABCO (5) THF 50 LDA (1.5) 30 Hydrochloric acid 5h/69/ 218 DMAP (10) MeCN 25 LDA (1.5) 30 Hydrochloric acid 5i/67/ 219 KI (10) MeCN 25 LDA (1.5) 30 Hydrochloric acid 5j/75/ 220 TiCl.sub.4 (0.5) toluene 0 LDA (1.5) 30 Hydrochloric acid 5k/58/ 221 ZnI.sub.2 (0.5) MeCN 25 LDA (1.5) 30 Hydrochloric acid 5l/60/ 222 Et/Me/Cl Zn(OTf).sub.2 (1) toluene 25 LDA Hydrochloric 5m/68/ (1.5) 30 acid 223 i-Pr/Me/Cl Zn(OTf).sub.2 (1) toluene 25 LDA Hydrochloric 5n/66/ (1.5) 30 acid 224 CyCH.sub.2/Et/Cl Zn(OTf).sub.2 (0.1) MeCN 25 LDA Hydrochloric 5o/70/ (1.5) 30 acid 225 CyCH.sub.2/Allyl/Cl K.sub.2CO.sub.3 (1) MeCN 50 LDA Hydrochloric 5p/48/ (1.5) 30 acid 226 BnCH.sub.2/Me/Cl IC1 (10) (R.sup.4 = OEt) Et.sub.2O 25 LDA Hydrochloric 5a/68/95 (1.5) 30 acid 227 BnCH.sub.2/Et/Cl IC1 (10) (R.sup.4 = OEt) MeCN 25 LDA Hydrochloric 5b/64/89 (1.5) 30 acid 228 BnCH.sub.2/i-Pr/Cl IC1 (10) (R.sup.4 = OEt) MeCN 50 LDA Hydrochloric 5c/58/78 (1.5) 30 acid 229 IC1 (10) (R.sup.4 = OEt) Et.sub.2O 25 LDA (1.5) 30 Hydrochloric acid 5d/62/85 230 IC1 (20) (R.sup.4 = OEt) THF 25 LDA (1.5) 30 Hydrochloric acid 5e/58/87 231 4-ClC.sub.6H.sub.4/Me/Cl IC1 (10) (R.sup.4 = OEt) THF 40 LDA Hydrochloric 5f/65/94 (1.5) 30 acid 232 4-MeC.sub.6H.sub.4/Me/Cl IC4 (20) THF 0 LDA Hydrochloric 5g/59/90 (1.5) 30 acid 233 0 IC1 (10) (R.sup.4 = OEt) THF 50 LDA (1.5) 30 Hydrochloric acid 5h/68/90 234 IC1 (10) (R.sup.4 = OEt) MeCN 25 LDA (1.5) 30 Hydrochloric acid 5i/72/89 235 IC1 (10) (R.sup.4 = OEt) CH.sub.2Cl.sub.2 25 LDA (1.5) 30 Hydrochloric acid 5j/70/90 236 IC1 (10) (R.sup.4 = OEt) toluene 0 LDA (1.5) 30 Hydrochloric acid 5k/60/86 237 IC2 (10) (X.sup.1 = NTf.sub.2) MeCN 25 LDA (1.5) 30 Hydrochloric acid 5l/58/80 238 Et/Me/Cl IC1 (10) (R.sup.4 = OEt) Et.sub.2O 25 LDA Hydrochloric 5m/70/90 (1.5) 30 acid 239 i-Pr/Me/Cl IC1 (10) (R.sup.4 = OEt) Et.sub.2O 25 LDA Hydrochloric 5n/66/94 (1.5) 30 acid 240 CyCH.sub.2/Et/Cl IC1 (10) (R.sup.4 = OEt) Et.sub.2O 50 LDA Hydrochloric 5o/65/85 (1.5) 30 acid 241 Cy/Allyl/Cl IC1 (10) (R.sup.4 = OEt) Et.sub.2O 25 LDA Hydrochloric 5p/58/95 (1.5) 30 acid

(188) The characterizations of 5a-5p are as follows:

(189) ##STR00165##

(190) .sup.1H NMR (400 MHz, CDCl.sub.3): 7.30-7.27 (m, 2H), 7.22-7.14 (m, 3H), 4.42 (dd, 1H), 4.39 (dd, 1H), 3.10 (s, br, 1H), 2.76-2.73 (m, 1H), 2.48-2.47 (m, 1H), 2.09-2.03 (m, 2H), 1.45 (s, 3H); .sup.13C NMR (100 MHz, CDCl.sub.3): 205.88, 140.88, 128.67, 128.43, 126.34, 79.43, 45.48, 41.90, 29.83, 26.16;

(191) ##STR00166##

(192) .sup.1H NMR (400 MHz, CDCl.sub.3): 7.32-7.26 (m, 2H), 7.20-7.13 (m, 3H), 4.42 (dd, 1H), 4.39 (dd, 1H), 3.10 (s, br, 1H), 2.78-2.75 (m, 1H), 2.48-2.47 (m, 1H), 1.83 (q, 2H), 0.95 (t, 3H); .sup.13C NMR (100 MHz, CDCl.sub.3): 205.88, 140.88, 128.67, 128.43, 126.34, 79.43, 45.48, 41.90, 29.83, 26.16;

(193) ##STR00167##

(194) .sup.1H NMR (400 MHz, CDCl.sub.3): 7.33-7.25 (m, 2H), 7.21-7.14 (m, 3H), 4.42 (dd, 1H), 4.39 (dd, 1H), 3.14 (s, br, 1H), 2.78-2.75 (m, 1H), 2.48-2.47 (m, 1H), 1.89-1.81 (q, 1H), 0.95 (d, 3H); .sup.13C NMR (100 MHz, CDCl.sub.3): 213.54, 140.87, 128.91, 128.43, 126.57, 85.61, 46.74, 33.13, 30.70, 27.81, 16.69;

(195) ##STR00168##

(196) .sup.1H NMR (400 MHz, CDCl.sub.3): 7.33-7.25 (m, 2H), 7.21-7.14 (m, 3H), 5.92 (dd, 1H), 5.30-5.05 (m, 1H), 4.42 (dd, 1H), 4.39 (dd, 1H), 3.16 (s, br, 1H), 2.78-2.75 (m, 1H), 2.48-2.47 (m, 1H); .sup.13C NMR (100 MHz, CDCl.sub.3): 207.22, 143.05, 140.87, 128.91, 128.43, 126.57, 118.08, 77.54, 46.08, 35.61, 32.84;

(197) ##STR00169##

(198) .sup.1H NMR (400 MHz, CDCl.sub.3): 7.32-7.24 (m, 2H), 7.21-7.14 (m, 3H), 4.42 (dd, 1H), 4.39 (dd, 1H), 3.17 (s, br, 1H), 2.68-2.60 (m, 1H), 2.48-2.47 (m, 1H), 1.80 (s, 1H); .sup.13C NMR (100 MHz, CDCl.sub.3): 213.74, 140.87, 128.91, 128.43, 126.57, 75.70, 73.78, 69.54, 45.36, 39.10, 33.22, 7.30;

(199) ##STR00170##

(200) .sup.1H NMR (400 MHz, CDCl.sub.3): 7.38 (m, 4H), 4.40 (dd, 1H), 4.32 (dd, 1H), 3.56 (s, br, 1H), 1.78 (s, 3H); .sup.13C NMR (100 MHz, CDCl.sub.3): 202.91, 139.26, 134.61, 129.13, 126.89, 80.16, 45.18, 26.14;

(201) ##STR00171##

(202) .sup.1H NMR (400 MHz, CDCl.sub.3): 7.30-7.05 (m, 4H), 4.30 (dd, 1H), 4.22 (dd, 1H), 3.36 (s, br, 1H), 2.34 (s, 3H), 1.78 (s, 3H); .sup.13C NMR (100 MHz, CDCl.sub.3): 202.91, 139.26, 134.61, 129.13, 126.89, 80.16, 45.18, 26.14;

(203) ##STR00172##

(204) .sup.1H NMR (400 MHz, CDCl.sub.3): 8.10-7.95 (m, 2H), 7.65-7.55 (m, 2H), 7.45 (s, 1H), 7.30 (d, 1H), 4.32 (dd, 1H), 4.25 (dd, 1H), 3.38 (s, br, 1H), 1.88 (s, 3H); .sup.13C NMR (100 MHz, CDCl.sub.3): 205.09, 146.27, 134.44, 134.11, 130.55, 129.46, 127.57 (d, J=6.1 Hz), 126.56 (d, J=18.2 Hz), 125.97, 79.45, 45.05, 24.85;

(205) ##STR00173##

(206) .sup.1H NMR (400 MHz, CDCl.sub.3): 7.05 (s, 1H), 6.55 (s, 1H), 4.55 (s, 2H), 4.30 (s, 2H), 4.12 (dd, 1H), 4.05 (dd, 1H), 3.38 (s, br, 1H), 1.88 (s, 3H); .sup.13C NMR (100 MHz, CDCl.sub.3): 205.09, 147.89, 142.43, 128.97, 122.55, 121.74, 112.84, 79.08, 61.57, 45.05, 24.85;

(207) ##STR00174##

(208) .sup.1H NMR (400 MHz, CDCl.sub.3): 7.03 (s, 1H), 6.85 (s, 1H), 6.30 (s, 2H), 4.12 (dd, 1H), 4.05 (dd, 1H), 3.58 (s, br, 1H), 1.89 (s, 3H); .sup.13C NMR (100 MHz, CDCl.sub.3): 205.09, 148.50, 146.18, 135.49, 123.04, 116.17, 107.96, 101.95, 79.08, 45.05, 24.85;

(209) ##STR00175##

(210) .sup.1H NMR (400 MHz, CDCl.sub.3): 7.63 (d, 1H), 6.55 (dd, 1H), 6.39 (d, 1H), 4.10 (dd, 1H), 4.00 (dd, 1H), 3.54 (s, br, 1H), 1.69 (s, 3H); .sup.13C NMR (100 MHz, CDCl.sub.3): 214.78, 158.50, 142.80, 112.07, 105.50, 75.98, 45.28, 23.37;

(211) ##STR00176##

(212) .sup.1H NMR (400 MHz, CDCl.sub.3): 6.35 (d, 1H), 6.09 (dd, 1H), 4.10 (dd, 1H), 4.00 (dd, 1H), 3.54 (s, br, 1H), 1.69 (s, 3H); .sup.13C NMR (100 MHz, CDCl.sub.3): 214.78, 155.72, 150.21, 111.01, 108.25, 75.10, 45.28, 23.37, 14.79;

(213) ##STR00177##

(214) .sup.1H NMR (400 MHz, CDCl.sub.3): 4.45 (dd, 2H), 2.97 (s, br, 1H), 1.81-1.67 (m, 2H), 1.39 (s, 3H), 0.86 (t, 3H); .sup.13C NMR (100 MHz, CDCl.sub.3): 206.00, 79.86, 45.73, 33.02, 25.44, 7.71;

(215) ##STR00178##

(216) .sup.1H NMR (400 MHz, CDCl.sub.3): 4.47 (dd, 1H), 4.43 (dd, 1H), 2.90 (s, br, 1H), 1.99-1.92 (m, 1H), 1.33 (s, 3H), 0.96 (dd, 1.2 Hz, 3H), 0.79 (d, 3H); .sup.13C NMR (100 MHz, CDCl.sub.3): 206.56, 81.69, 46.13, 35.49, 23.70, 17.08, 15.86;

(217) ##STR00179##

(218) .sup.1H NMR (400 MHz, CDCl.sub.3): 4.43 (dd, 1H), 4.37 (dd, 1H), 3.12 (s, br, 1H), 1.72-1.56 (m, 8H), 1.50-1.47 (m, 1H), 1.39-1.32 (m, 1H), 1.25-1.06 (m, 3H), 1.11-0.86 (m, 2H), 0.81 (t, 3H); .sup.13C NMR (100 MHz, CDCl.sub.3): 206.36, 82.67, 46.64, 46.06, 34.94, 34.39, 33.53, 33.36, 26.29, 26.27, 26.13, 7.49;

(219) ##STR00180##

(220) .sup.1H NMR (400 MHz, CDCl.sub.3): 5.73-5.66 (m, 1H), 5.19-5.13 (m, 2H), 4.43 (s, 2H), 3.02 (s, 1H), 2.50-2.40 (m, 2H), 1.76-1.60 (m, 6H), 1.54-1.50 (m, 1H), 1.43-1.36 (m, 1H), 1.28-1.08 (m, 3H), 1.01-0.83 (m, 2H); .sup.13C NMR (100 MHz, CDCl.sub.3): 205.83, 131.52, 120.41, 82.10, 46.80, 46.55, 44.77, 34.88, 34.39, 34.47, 26.29, 26.26, 26.13.

(221) 8) Total Synthesis of the Colorado Potato Beetle Aggregation Pheromone (Table 8).

(222) ##STR00181##

(223) General procedure 8: the catalyst IC1 (R is OEt), ketone 6 (40.0 mmol) and a corresponding solvent (40 mL) were added into a dry Schlenk tube (25 mL). After being stirred at 30 C. for 0.5 h, 1aa (60 mmol) was added to the mixture. The process of the reaction was monitored by TLC analysis. After the consumption of the raw material 6 was complete, crude product 7 was obtained by filtering the reaction mixture by 5 cm silica gel column, eluting with Et.sub.2O, and removing the solvent under reduced pressure. Then the crude product 7 was transferred to a dry Schlenk tube (150 mL) and dissolved with anhydrous THF (40 mL). The mixture was stirred at 30 C. for 0.5 h, and then base LDA (60 mmol) was added dropwise slowly. The process of the reaction was monitored by TLC analysis. After the consumption of the raw material 7 was complete, the reaction mixture was quenched by 20 mL hydrochloric acid (4 M), and extracted three times by EtOAc. Crude 8 was obtained by combing the organic phase, and rotary evaporation of the solvent and dried under vacuum.

(224) Then, the crude 8 was dissolved with tetrahydrofuran (40 mL), and then added KOAc (45 mmol). The mixture was refluxed at 100 C. and the process of the reaction was monitored by TLC analysis. After the 8 was converted completely, the reaction mixture was rotary evaporated to remove the solvent. Then saturated ammonium chloride (40 mL) and ethyl acetate (60 mL) was added for liquid separation, After phase separation, the aqueous phase was extracted with ethyl acetate (40 mL*2). The organic phase combined, dried with anhydrous sodium sulfate and rotary evaporated to remove the solvent to provide light brown oily liquid.

(225) Next, the light brown oily liquid was dissolved in methanol (40 mL), and added K.sub.2CO.sub.3 (45 mmol) while stirring. The resulting solution was heated to reflux at 100 C. oil bath until the corresponding intermediate was converted completely by TLC analysis. The reaction mixture was then rotary evaporated to remove MeOH under reduced pressure. Saturated ammonium chloride (40 mL) and ethyl acetate (60 mL) were added. After phase separation, the aqueous phase was extracted with ethyl acetate (20 mL*2). The organic phase was combined and dried with anhydrous sodium sulfate. After rotary evaporation of the solvent, the resulted light brown oily liquid was subjected to column chromatography to afford pure(S)CPB as shown in (IV).

(226) The specific experimental operations of the examples 242-243 are referred to general procedure 8. The specific reaction conditions and yield of each example are shown in Table 8.

(227) TABLE-US-00008 TABLE 8 Specific reaction conditions and yields of the example 242-243. Example Z Yield (%) Ee (%) 242 Cl 65 97 243 Br 53 96

(228) The characterization of(S)CPB is as follows:

(229) ##STR00182##

(230) .sup.1H NMR (400 MHz, CDCl.sub.3): 5.04 (t, 1H), 4.54-4.43 (m, 2H), 2.94 (s, br, 2H), 2.14-2.05 (m, 1H), 1.95-1.87 (m, 1H), 1.83-1.71 (m, 2H), 1.67 (s, 3H), 1.58 (s, 3H), 1.37 (s, 3H); .sup.13C NMR (100 MHz, CDCl.sub.3): 214.25, 133.39, 123.07, 78.58, 64.76, 40.03, 26.20, 25.71, 22.26, 17.76;

(231) 9) Tandem Cyanosilylation Reaction/Ring-Closing Olefin Metathesis of Cyansilane Lab (Table 9).

(232) ##STR00183##

(233) General procedure 9: the catalyst I (0.05 mmol), a raw material 9 (1.0 mmol) and a corresponding solvent (1 mL) were added into a dry Schlenk tube (25 mL). The mixture was added with 1ab (1.5 mmol) after being stirred at a corresponding temperature for 0.5 h. The progress of the reaction was monitored by TLC analysis. After the consumption of the raw material 9 was complete, crude product 10 was obtained by filtering the reaction mixture by 5 cm silica gel column, eluting with Et.sub.2O, and removing solvent under reduced pressure. The crude product 10 was transferred to a dry Schlenk tube (25 mL) and dissolved with anhydrous CH.sub.2C12 (2.0 mL), and added with catalyst Grubbs I (0.01 mmol) at 25 C. The progress of the reaction was monitored by TLC analysis. After the consumption of the 10 was complete, the desired product 11 as shown in Scheme (V) was obtained from the reaction mixture by column chromatography directly.

(234) The specific experimental operations of the examples 244-255 are shown in general procedure 9. The specific reaction conditions and yield of each example are shown in Table 9.

(235) TABLE-US-00009 TABLE 9 Specific reaction conditions and yields of the examples 244-255. Example n R.sup.6 Catalyst I Product Yield (%)/Ee (%) 244 0 Me K.sub.2CO.sub.3 11a 75/ 245 1 Me K.sub.2CO.sub.3 11b 73/ 246 4 Me K.sub.2CO.sub.3 11c 69/ 247 1 H K.sub.2CO.sub.3 11b 60/ 248 1 Et K.sub.2CO.sub.3 11b 70/ 249 1 Ph K.sub.2CO.sub.3 11b 78/ 250 0 Me IC1 11a 68/96 (R.sup.4 = OEt) 251 1 Me IC1 11b 70/95 (R.sup.4 = OEt) 252 4 Me IC1 11c 75/92 (R.sup.4 = OEt) 253 1 H IC1 11b 60/90 (R.sup.4 = OEt) 254 1 Et IC1 11b 77/96 (R.sup.4 = OEt) 255 1 Ph IC1 11b 73/92 (R.sup.4 = OEt)

(236) The characterizations of 11a-11c are as follows:

(237) ##STR00184##

(238) .sup.1H NMR (400 MHz, CDCl.sub.3): 5.84 (d, 1H), 5.43 (d, 1H), 1.81 (s, 3H), 0.35 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 152.92, 134.94, 117.46, 81.92, 27.70, 2.22;

(239) ##STR00185##

(240) .sup.1H NMR (400 MHz, CDCl.sub.3): 5.68-5.61 (m, 2H), 2.03 (d, 2H), 1.87 (s, 3H), 0.33 (s, 6H); (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 152.04, 136.84, 118.40, 81.92, 75.78, 27.40, 2.82;

(241) ##STR00186##

(242) .sup.1H NMR (400 MHz, CDCl.sub.3): 5.67-5.60 (m, 2H), 2.03 (m, 2H), 1.87 (s, 3H), 1.44-1.30 (m, 6H), 0.35 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 137.26, 131.80, 119.50, 75.58, 30.97, 30.00, 29.38, 23.57, 15.78, 2.48.

(243) 10) Epoxy Ring-Opening Reaction/Functional Mass Transfer Reaction of Functionalized Silyl Cyanide 1aa (Table 10).

(244) ##STR00187##

(245) General procedure 10: the catalyst I, a raw material 12 (1.0 mmol) and a corresponding solvent (1 mL) were added into a dry Schlenk tube (25 mL). The mixture was added with 1aa (1.5 mmol) after being stirred at a corresponding temperature for 0.5 h. The process of the reaction was monitored by TLC analysis. After the consumption of the raw material 12 was complete, crude product 13 was obtained by filtering the reaction mixture by 5 cm silica gel column, eluting with Et2O, and removing solvent under reduced pressure. The crude product 13 was transferred to a dry Schlenk tube (25 mL) and dissolved with anhydrous THF (4.0 mL). The resulting solution was stirred at 30 C. for 0.5 h, and then LDA (1.5 mmol) was added dropwise slowly. The progress of the reaction was monitored by TLC analysis. After the consumption of the 13 was complete, the reaction mixture was quenched by 5 mL hydrochloric acid (4 M), and then extracted three times by EtOAc. The desired product 14 as shown in Scheme (III) was obtained by combing the organic phase, rotary evaporating to remove the solvent and column chromatography.

(246) The specific experimental operations of the examples 256-286 are referred to general procedure 10. The specific reaction conditions and yield of each example are shown in Table 10.

(247) TABLE-US-00010 TABLE 10 Specific reaction conditions and yields of the examples 256-286 Product/Yield Example R.sup.7/R.sup.8/R.sup.9/Z Catalyst I (mol %) Solvent T1 ( C.) (%)/Ee (%) 256 Ph/Me/Me/ Na.sub.2CO.sub.3 (5) MeCN 25 14a/63/ Cl 257 Ph/Me/Me/ Li.sub.2CO.sub.3 (5) MeCN 25 14a/64/ Cl 258 Ph/Me/Me/ Na.sub.2CO.sub.3 (5) MeCN 25 14a/70/ Cl 259 Ph/Me/Me/ CsOAc (25) MeCN 25 14a/63/ Cl 260 Ph/Me/Me/ Et.sub.3N (5) MeCN 25 14a/68/ Cl 261 Ph/Me/Me/ Zn(OTf).sub.2 (0.1) MeCN 25 14a/73/ Cl 262 Ph/Me/Me/ KI (10) MeCN 25 14a/66/ Cl 263 Ph/Me/Me/ TiCl.sub.4 (0.5) MeCN 25 14a/65/ Cl 264 Ph/Me/Me/ ZnI.sub.2 (0.5) MeCN 25 14a/65/ Cl 265 Bn/Me/Me/ Na.sub.2CO.sub.3 (5) MeCN 25 14b/71/ Cl 266 BnCH.sub.2/Me/ Na.sub.2CO.sub.3 (5) MeCN 25 14c/75/ Cl 267 BnCH.sub.2/Me/ Na.sub.2CO.sub.3 (5) MeCN 25 14d/65/ Br 268 Et/allyl/allyl/ Na.sub.2CO.sub.3 (5) MeCN 25 14e/65/ Cl 269 Ph/Et/Et/Cl Na.sub.2CO.sub.3 (5) MeCN 40 14f/68/ 270 Ph/Allyl/Allyl/ Na.sub.2CO.sub.3 (5) MeCN 35 14g/66/ Cl 271 Ph/H/H/Cl Na.sub.2CO.sub.3 (5) MeCN 25 14h/38/ 272 Ph/Et/Me/Cl Na.sub.2CO.sub.3 (5) MeCN 25 14i/33/ 273 Ph/Allyl/Me/ Na.sub.2CO.sub.3 (5) MeCN 25 14j/35/ Cl 274 Ph/Me/Me/ IC1 (R.sup.4 = Me) Et.sub.2O 25 14a/33/87 Cl 275 Ph/Me/Me/ IC1 (R.sup.4 = OEt) Et.sub.2O 30 14a/40/92 Cl 276 Ph/Me/Me/ IC1 (R.sup.4 = H) Et.sub.2O 30 14a/31/85 Cl 277 Ph/Me/Me/ IC1 (R.sup.4 = Ot-Bu) Et.sub.2O 30 14a/37/90 Cl 278 Bn/Me/Me/ IC1 (R.sup.4 = OEt) Et.sub.2O 30 14b/38/85 Cl 279 BnCH.sub.2/Me/ IC1 (R.sup.4 = OEt) Et.sub.2O 30 14c/42/80 Cl 280 BnCH.sub.2/Me/ IC1 (R.sup.4 = OEt) Et.sub.2O 30 14d/35/82 Br 281 Et/allyl/allyl/ IC1 (R.sup.4 = OEt) Et.sub.2O 30 14e/35/75 Cl 282 Ph/Et/Et/Cl IC1 (R.sup.4 = OEt) Et.sub.2O 30 14f/35/73 283 Ph/Allyl/Allyl/ IC1 (R.sup.4 = OEt) Et.sub.2O 30 14g/36/70 Cl 284 Ph/H/H/Cl IC1 (R.sup.4 = OEt) Et.sub.2O 30 14h/28/67 285 Ph/Et/Me/Cl IC1 (R.sup.4 = OEt) Et.sub.2O 30 14i/39/80 286 Ph/Allyl/Me/ IC1 (R.sup.4 = OEt) Et.sub.2O 30 14j/38/85 Cl

(248) The characterizations of compounds 14a-14j are as follows:

(249) ##STR00188##

(250) .sup.1H NMR (400 MHz, CDCl.sub.3): 7.50-7.38 (m, 2H), 7.22-7.14 (m, 3H), 4.42 (dd, 2H), 3.7 (s, 1H), 3.12 (s, br, 1H), 1.67 (s, 3H), 1.26 (s, 3H); .sup.13C NMR (100 MHz, CDCl.sub.3): 197.94, 139.14, 131.28, 128.97, 127.91, 74.88, 70.58, 50.52, 26.81;

(251) ##STR00189##

(252) .sup.1H NMR (400 MHz, CDCl.sub.3): 7.40-7.35 (m, 2H), 7.29-7.17 (m, 3H), 4.52 (dd, 2H), 3.12 (s, br, 1H), 3.09 (dd, 1H), 2.84-2.80 (m, 2H), 1.67 (s, 3H), 1.26 (s, 3H); .sup.13C NMR (100 MHz, CDCl.sub.3): 202.81, 137.81, 129.07, 128.73, 127.06, 75.93, 63.52, 49.53, 28.58, 27.87;

(253) ##STR00190##

(254) .sup.1H NMR (400 MHz, CDCl.sub.3): 7.42-7.30 (m, 2H), 7.28-7.15 (m, 3H), 4.54 (dd, 2H), 3.15 (s, br, 1H), 2.55 (t, 2H), 2.40 (t, 1H), 1.86 (1, 2H), 1.67 (s, 3H), 1.25 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 207.26, 141.62, 129.07, 128.37, 126.35, 76.10, 57.27, 49.53, 35.95, 28.58, 25.75;

(255) ##STR00191##

(256) .sup.1H NMR (400 MHz, CDCl.sub.3): 7.44-7.31 (m, 2H), 7.27-7.14 (m, 3H), 4.46 (dd, 2H), 3.18 (s, br, 1H), 2.56 (t, 2H), 2.43 (t, 1H), 1.85 (1, 2H), 1.67 (s, 3H), 1.27 (s, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 206.07, 141.62, 129.07, 128.37, 126.35, 76.10, 60.50, 38.06, 35.95, 28.58, 25.75;

(257) ##STR00192##

(258) .sup.1H NMR (400 MHz, CDCl.sub.3): 5.94-5.81 (m, 2H), 5.17-4.94 (m, 4H), 4.47 (dd, 2H), 3.58 (s, br, 1H), 2.58 (q, 1H), 2.13 (d, 2H), 1.67 (s, 3H), 1.15 (d, 3H); .sup.13C NMR (100 MHz, CDCl.sub.3): 198.64, 133.18, 119.40, 73.02, 52.25, 48.49, 47.30, 10.56;

(259) ##STR00193##

(260) .sup.1H NMR (400 MHz, CDCl.sub.3): 7.47-7.39 (m, 2H), 7.32-7.14 (m, 3H), 4.41 (dd, 2H), 3.73 (s, 1H), 3.15 (s, br, 1H), 1.67 (s, 3H), 1.55 (q, 4H), 0.96 (t, 6H); .sup.13C NMR (100 MHz, CDCl.sub.3): 198.74, 138.38, 131.51, 128.96, 127.79, 72.56, 65.98, 50.52, 31.54, 7.62;

(261) ##STR00194##

(262) .sup.1H NMR (400 MHz, CDCl.sub.3): 7.47-7.39 (m, 2H), 7.32-7.14 (m, 3H), 5.94-5.81 (m, 2H), 5.17-4.94 (m, 4H), 4.42 (dd, 2H), 3.73 (s, 1H), 3.15 (s, br, 1H), 2.05 (d, 4H), 1.67 (s, 3H); .sup.13C NMR (100 MHz, CDCl.sub.3): 198.74, 138.38, 133.18, 131.51, 128.96, 127.79, 119.40, 72.78, 69.84, 50.52, 44.59;

(263) ##STR00195##

(264) .sup.1H NMR (400 MHz, CDCl.sub.3): 7.45-7.33 (m, 2H), 7.27-7.14 (m, 3H), 4.45 (dd, 2H), 4.23 (dd, 1H), 3.95 (dd, 1H), 3.65 (s, br, 1H), 1.67 (s, 3H); .sup.13C NMR (100 MHz, CDCl.sub.3): 189.78, 137.59, 130.52, 128.69, 128.24, 66.24, 55.33, 51.14;

(265) ##STR00196##

(266) .sup.1H NMR (400 MHz, CDCl.sub.3): 7.46-7.38 (m, 2H), 7.33-7.15 (m, 3H), 4.41 (dd, 2H), 3.74 (s, 1H), 3.45 (s, br, 1H), 1.67 (s, 3H), 1.53 (q, 2H), 1.23 (s, 3H), 0.95 (t, 3H); .sup.13C NMR (100 MHz, CDCl.sub.3): 199.25, 138.12, 131.06, 128.93, 127.66, 72.93, 65.48, 50.52, 33.39, 23.22, 7.41;

(267) ##STR00197##

(268) .sup.1H NMR (400 MHz, CDCl.sub.3): 7.47-7.39 (m, 2H), 7.32-7.14 (m, 3H), 5.90-5.80 (m, 1H), 5.19-4.92 (m, 2H), 4.45 (dd, 2H), 3.75 (s, 1H), 3.35 (s, br, 1H), 2.05 (dd, 1H); 1.95 (dd, 1H), 1.67 (s, 3H), 1.36 (s, 3H); .sup.13C NMR (100 MHz, CDCl.sub.3): 199.25, 138.12, 133.16, 131.06, 128.93, 127.66, 119.35, 74.20, 68.20, 50.52, 45.79, 24.04.

(269) It will be apparent to those skilled in the art that modifications and variations can be made without departing from the scope and spirit disclosed by the appended claims of the present disclosure, and such modifications and variations all fall in the protection extent of the claims of the present disclosure.