Tributylvinyltin → HCID 45378233, compound

HRID 1511570Notes

Reaction equation

HRID 1511570 reaction equation
FC(F)(F)S(O[C:7]1[CH:8]=[CH:9][CH:10]=[C:11]2[C:16]=1[CH2:15][N:14]([C:17]([O:19][C@H:20]1[CH2:24][N:23]([C:25]([O:27][C:28]([CH3:31])([CH3:30])[CH3:29])=[O:26])[C@H:22]([C:32]([O:34][CH3:35])=[O:33])[CH2:21]1)=[O:18])[CH2:13][CH2:12]2)(=O)=O.[CH2:38]([Sn](CCCC)(CCCC)C=C)[CH2:39]CC.[Cl-].[Li+]>CN(C=O)C.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.Cl[Pd]Cl>[CH:38]([C:7]1[CH:8]=[CH:9][CH:10]=[C:11]2[C:16]=1[CH2:15][N:14]([C:17]([O:19][C@H:20]1[CH2:24][N:23]([C:25]([O:27][C:28]([CH3:30])([CH3:29])[CH3:31])=[O:26])[C@H:22]([C:32]([O:34][CH3:35])=[O:33])[CH2:21]1)=[O:18])[CH2:13][CH2:12]2)=[CH2:39]

Participants

6

Reactant 3

HCID 81998TributylvinyltinHCID 433294Lithium ChlorideHCID 45378374HCID 45378374, compound

Product 1

HCID 45378233HCID 45378233, compoundYield 159.1%

Reagents, catalysts & solvents 2

HCID 6102075Dichlorobis(triphenylphosphine)palladiumCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
25 °C

Procedure

A solution of 1-tert-butyl 2-methyl (2S,4R)-4-({[8-{[(trifluoromethyl)sulfonyl]oxy}-3,4-dihydroisoquinolin-2(1H)-yl]carbonyl}oxy)pyrrolidine-1,2-dicarboxylate (1.74 g, 3.15 mmol), tri-n-butyl vinyl tin (1.10 g, 1.46 mmol) and lithium chloride (0.40 g, 9.45 mmol) in 25 mL DMF was purged with nitrogen for 10 min. Then bis(triphenylphosphine)palladium (II) chloride (0.22 g, 0.32 mmol) was added, and the mixture stirred at 25° C. under nitrogen for 18 h. The mixture was partitioned between EtOAc and saturated NaHCO3, the organic layer separated and washed with water then brine, dried over anhydrous sodium sulfate and concentrated to an oil. The oil was purified by column chromatography on silica gel (gradient elution, 10 to 65% EtOAc in hexanes) to give a colorless oil, 1-tert-butyl 2-methyl (2S,4R)-4-{[(8-vinyl-3,4-dihydroisoquinolin-2(1H)-yl)carbonyl]oxy}pyrrolidine-1,2-dicarboxylate (1.00 g, 74% yield). LRMS (ESI) m/z 453.2 [(M+Na)+; calcd for C23H30N2O6Na: 453.5].

Workup

  1. customThe mixture was partitioned between EtOAc and saturated NaHCO3
  2. customthe organic layer separated
  3. washwashed with water
  4. dry with materialbrine, dried over anhydrous sodium sulfate
  5. concentrationconcentrated to an oil
  6. customThe oil was purified by column chromatography on silica gel (gradient elution, 10 to 65% EtOAc in hexanes)

Sources & evidence

ORD record
ord-fd4467287df54a8090ece4c74bd32f45
Source dataset
uspto-grants-2012_07
Patent number
US08216999B2

Reaction notes

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