Methyl morpholine oxide → 5-oxo-6-propyl-3,3a,4,5-tetrahydro-1H-cyclopenta[c]pyrrole-2-carboxylic acid tert-butyl ester

HRID 130376Notes

Reaction equation

HRID 130376 reaction equation
[C:1]([O:5][C:6](=[O:17])[N:7]([CH2:14][CH:15]=[CH2:16])[CH2:8][C:9]#[C:10][CH2:11][CH2:12][CH3:13])([CH3:4])([CH3:3])[CH3:2].C[N+]1([O-])CC[O:22][CH2:21]C1>ClCCl.[CH-]=O.[CH-]=O.[C-]#[O+].[C-]#[O+].[C-]#[O+].[C-]#[O+].[C-]#[O+].[C-]#[O+].[Co].[Co+2]>[C:1]([O:5][C:6]([N:7]1[CH2:14][CH:15]2[CH2:16][C:21](=[O:22])[C:10]([CH2:11][CH2:12][CH3:13])=[C:9]2[CH2:8]1)=[O:17])([CH3:3])([CH3:2])[CH3:4]

Participants

5

Reactant 2

HCID 82029Methyl morpholine oxideHCID 86600396Allyl-hex-2-ynyl-carbamic acid tert-butyl ester

Product 1

HCID 692253565-oxo-6-propyl-3,3a,4,5-tetrahydro-1H-cyclopenta[c]pyrrole-2-carboxylic acid tert-butyl esterYield 38.8%

Reagents, catalysts & solvents 2

HCID 25049Dicobalt Octacarbonyl (stabilized with 1-5% Hexane)CatalystHCID 6344DichloromethaneSolvent

Procedure

A solution of allyl-hex-2-ynyl-carbamic acid tert-butyl ester (741 mg, 3.12 mmol) in dichloromethane (50 mL) was added to dicobalt octacarbonyl (1.12 g, 3.28 mmol) under an argon atmosphere. The resulting solution was stirred at room temperature for 1.5 h. After this time, N-methylmorpholine N-oxide (2.56 g, 21.9 mmol) was added in portions during a 60 min period. Upon completion of addition, the reaction mixture was stirred for an additional 2.5 h. At the conclusion of this period, the mixture was filtered through silica gel, and the solid was washed with a 1:1 ethyl acetate-hexane solution (200 mL). The filtrate was concentrated under vacuum to yield a residue. The residue was purified by flash column chromatography to provide a light brown oil (321 mg, 38%). 1H NMR (400 MHz, CDCl3) δ 5.3-3.9 (m, 3H), 3.17 (m, 1H), 2.80 (m, 1H), 2.67 (m, 1H), 2.29 (m, 1H), 2.13 (m, 2H), 1.51 (m+2s, 11H), 0.91 (m, 3H). MS (ES+) m/z 266.19 (M+H+).

Workup

  1. additionUpon completion of addition
  2. stirringthe reaction mixture was stirred for an additional 2.5 h
  3. filtrationAt the conclusion of this period, the mixture was filtered through silica gel
  4. washthe solid was washed with a 1:1 ethyl acetate-hexane solution (200 mL)
  5. concentrationThe filtrate was concentrated under vacuum
  6. customto yield a residue
  7. customThe residue was purified by flash column chromatography

Sources & evidence

ORD record
ord-f4442d268346425d8e14694855f5fdc7
Source dataset
uspto-grants-2008_06
Patent number
US07381738B2

Reaction notes

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