Water → (2S)-2-[[[(1,1-Dimethylethyl)dimethylsilyl]oxy]methyl]-4-methylenepyrrolidine

HRID 915701Notes

Reaction equation

HRID 915701 reaction equation
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]

Participants

6

Reactant 3

HCID 962WaterHCID 5948TributylstannaneHCID 18639168(2S)-1-allyloxycarbonyl-2-(t-butyldimethylsilyloxymethyl)-4-methylenepyrrolidine

Product 1

HCID 58400350(2S)-2-[[[(1,1-Dimethylethyl)dimethylsilyl]oxy]methyl]-4-methylenepyrrolidine

Reagents, catalysts & solvents 2

HCID 178418476HCID 178418476, compoundCatalystHCID 6344DichloromethaneSolvent2×

Procedure

A catalytic amount of PdCl2(PPh3)2 (92 mg, 0.131 mmol) was added to a solution of the allyl carbamate 7 (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 8 as a slightly orange oil (0.56 g, 77%): [α]21D=−3.9° (c=5.0, CHCl3); 1H NMR (270 MHz, CDCl3) δ 4.93 (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) δ 150.0 (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═CH2), 2929, 2857, 1664 (C═C), 1472, 1424, 1391, 1380, 1361, 1255, 1190, 1101, 1006, 939, 880, 838, 777, 723, 668 cm−1.

Workup

  1. customA slightly exothermic reaction with vigorous gas evolution
  2. dry with materialthe organic solution was dried (MgSO4)
  3. filtrationfiltered
  4. customevaporated in vacuo
  5. customto give an orange oil which
  6. customwas purified by flash chromatography (50-100% EtOAc/Petroleum Ether)

Sources & evidence

ORD record
ord-4fc3dbe8be244a8893e22a65f1c13224
Source dataset
uspto-grants-2007_09
Patent number
US07265105B2

Reaction notes

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