C(OC([N:7]1[CH2:11][C:10](=[CH2:12])[CH2:9][C@H:8]1[CH2:13][O:14][Si:15]([C:18]([CH3:21])([CH3:20])[CH3:19])([CH3:17])[CH3:16])=O)C=C.O.CCCC[SnH](CCCC)CCCC>C(Cl)Cl.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[Si:15]([O:14][CH2:13][C@@H:8]1[CH2:9][C:10](=[CH2:12])[CH2:11][NH:7]1)([C:18]([CH3:21])([CH3:20])[CH3:19])([CH3:16])[CH3:17]
A catalytic amount of PdCl2(PPh3)2 (92 mg, 0.131 mmol) was added to a solution of the allyl carbamate 57 (1.0 g, 3.22 mmol) and H2O (0.34 mL, 18.9 mmol) in CH2Cl2 (30 mL). After 5 minutes stirring at room temperature, Bu3SnH (0.96 mL, 1.04 g, 3.57 mmol) was added rapidly in one portion. A slightly exothermic reaction with vigorous gas evolution immediately ensued. The mixture was stirred for 16 hours at room temperature under nitrogen at which point TLC (50% EtOAc/Petroleum Ether) revealed the formation of amine. After diluting with CH2Cl2 (30 mL), the organic solution was dried (MgSO4), filtered and evaporated in vacuo to give an orange oil which was purified by flash chromatography (50-100% EtOAc/Petroleum Ether) to afford the amine 58 as a slightly orange oil (0.56 g, 77%): [α]21D=−3.9° (c=5.0, CHCl3); 1H NMR (270 MHz, CDCl3) δ4.93 (t, 1H, J=2.02 Hz, NCH2C═CH2), 4.90 (t, 1H, J=2.02 Hz, NCH2C═CH2), 3.68-3.46 (m, 4H, NCHCH2OTBDMS and NCH2C═CH2), 3.30-3.21 (m, 1H, NCHCH2OTBDMS), 2.53-2.41 (m, 2H, NCH2C═CH2CH2 and NH), 2.26-2.17 (m, 1H, NCH2C═CH2CH2), 0.90 (s, 9H, SiC(CH3)3), 0.06 (s, 6H, Si(CH3)2); 13C NMR (67.8 MHz, CDCl3) δ150.0 (NCH2C═CH2), 104.7 (NCH2C═CH2), 64.7 (NCHCH2OTBDMS), 60.5 (NCHCH2OTBDMS), 51.3 (NCH2C═CH2), 34.9 (NCH2C═CH2CH2), 25.9 (SiC(CH3)3), 18.3 (SiC(CH3)3), −5.4 (Si(CH3)2); MS (EI), m/z (relative intensity) 227 (M+., 8), 212 (6), 170 (M—tBu, 36), 96 (8), 82 (M—CH2OTBDMS, 100), 75 (11); IR (Neat) 3550-3100 (br, NH), 3074 (C═CH12), 2929, 2857, 1664 (C═C), 1472, 1424, 1391, 1380, 1361, 1255, 1190, 1101, 1006, 939, 880, 838, 777, 723, 668 cm−1.
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