Water → HCID 69621513, compound

HRID 1830935Notes

Reaction equation

HRID 1830935 reaction equation
C(OC([N:7]1[CH:11]=[C:10]([CH2:12][C:13]([O:15][CH3:16])=[O:14])[CH2:9][C@H:8]1[CH2:17][O:18][Si:19]([C:22]([CH3:25])([CH3:24])[CH3:23])([CH3:21])[CH3:20])=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:19]([O:18][CH2:17][C@@H:8]1[CH2:9][C:10]([CH2:12][C:13]([O:15][CH3:16])=[O:14])=[CH:11][NH:7]1)([C:22]([CH3:25])([CH3:24])[CH3:23])([CH3:20])[CH3:21]

Participants

6

Reactant 3

HCID 962WaterHCID 5948TributylstannaneHCID 69621455HCID 69621455, compound

Product 1

HCID 69621513HCID 69621513, compound

Reagents, catalysts & solvents 2

HCID 178418476HCID 178418476, compoundCatalystHCID 6344DichloromethaneSolvent

Procedure

A catalytic amount of PdCl2(PPh3)2 (84 mg, 0.12 mmol) was added to a stirred solution of the allyl carbamate 17 (1.10 g, 2.98 mmol) and H2O (0.32 mL, 17.8 mmol) in CH2Cl2 (36 mL) After 5 minutes stirring at room temperature, Bu3SnH (0.89 mL, 0.96 g, 3.30 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 time TLC (50% EtOAc/Petroleum Ether) revealed the formation of amine along with the complete consumption of starting material. 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% EtOAc/Petroleum Ether) to afford the enamine 18 as a slightly orange oil (0.57 g, 67%): 1H NMR (270 MHz, CDCl3) δ7.53 and 7.48 (br s×2, 1H, NCH═CCH2CO2CH3), 4.35-4.13 (m, 1H, NCHCH2OTBDMS), 3.82-3.17 (m, 7H, NCH═CCH2CO2CH3, NCHCH2OTBDMS and CO2CH3), 2.64-2.04 (m, 2H, NCH═CCH2CO2CH3CH2), 0.90-0.88 (m, 9SiC(CH3)3), 0.09-0.00 (m, 6H, Si(CH3)2); MS (EI), m/z (relative intensity) 285 (M+., 1), 270 (M—CH3, 7), 254 (6), 242 (4), 230 (6), 228 (M—tBu, 100), 212 (4), 196 (3), 168 (13), 115 (3), 89 (10), 80 (4), 73 (13); MS (CI), m/z (relative intensity) 342 (M+.57, 7), 302 (M+. +17, 7), 286 (M+. +1, 100), 228 (M—tBu, 100).

Workup

  1. customA slightly exothermic reaction with vigorous gas evolution
  2. customalong with the complete consumption of starting material
  3. additionAfter diluting with CH2Cl2 (30 mL)
  4. dry with materialthe organic solution was dried (MgSO4)
  5. filtrationfiltered
  6. customevaporated in vacuo
  7. customto give an orange oil which
  8. customwas purified by flash chromatography (50% EtOAc/Petroleum Ether)

Sources & evidence

ORD record
ord-20e4e93adb9f445cab95e4201481134c
Source dataset
uspto-grants-2006_06
Patent number
US07067511B2

Reaction notes

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