Methyl morpholine oxide → tert-butyl 6-methyl-5-oxo-3,3a,4,5-tetrahydrocyclopenta[c]pyrrole-2(1H)-carboxylate

HRID 877689Notes

Reaction equation

HRID 877689 reaction equation
[CH2:1]([N:4]([CH2:12][C:13]#[C:14][CH3:15])[C:5](=[O:11])[O:6][C:7]([CH3:10])([CH3:9])[CH3:8])[CH:2]=[CH2:3].C[N+]1([O-])CC[O:20][CH2:19]C1>ClCCl.[CH-]=O.[CH-]=O.[C-]#[O+].[C-]#[O+].[C-]#[O+].[C-]#[O+].[C-]#[O+].[C-]#[O+].[Co].[Co+2]>[CH3:15][C:14]1[C:19](=[O:20])[CH2:3][CH:2]2[CH2:1][N:4]([C:5]([O:6][C:7]([CH3:8])([CH3:9])[CH3:10])=[O:11])[CH2:12][C:13]=12

Participants

5

Reactant 2

HCID 82029Methyl morpholine oxideHCID 11085062Tert-butyl allyl(but-2-yn-1-yl)carbamate

Product 1

HCID 15638530tert-butyl 6-methyl-5-oxo-3,3a,4,5-tetrahydrocyclopenta[c]pyrrole-2(1H)-carboxylateYield 63.2%

Reagents, catalysts & solvents 2

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

Procedure

Dicobalt octacarbonyl (28.1 g, 82 mmol) was added to a solution of tert-butyl allyl(but-2-yn-1-yl)carbamate (16.4 g, 78 mmol) in dichloromethane (700 mL) at room temperature. The resulting mixture was and stirred under nitrogen for 1.5 h at room temperature, then cooled to 0° C. N-methylmorpholine-N-oxide (55.1 g, 470 mmol) was added in small portions over 1 h. The resultant mixture was stirred at 0° C. for 1 h, at ambient temperature for 2 h and filtered through a silica gel pad. The filter cake was washed with 1:1 mixture of ethyl acetate and hexanes until free of product. The filtrate was concentrated. Silica gel chromatography, eluting with 20-45% ethyl acetate in hexanes, gave tert-butyl 6-methyl-5-oxo-3,3a,4,5-tetrahydrocyclopenta[c]pyrrole-2(1H)-carboxylate (11.7 g, 63% yield). 1H NMR (400 MHz, chloroform-d) δ ppm 4.18 (2 H, d, J=16.29 Hz), 3.92-4.14 (1 H, m), 2.97-3.25 (1 H, m), 2.73-2.87 (1 H, m), 2.52-2.73 (1 H, m), 2.08-2.26 (1 H, m), 1.77 (3 H, s), 1.49 (9 H, s).

Workup

  1. temperaturecooled to 0° C
  2. filtrationfiltered through a silica gel pad
  3. washThe filter cake was washed with 1:1 mixture of ethyl acetate and hexanes until free of product
  4. concentrationThe filtrate was concentrated
  5. washSilica gel chromatography, eluting with 20-45% ethyl acetate in hexanes

Sources & evidence

ORD record
ord-06f0daecf6bf4cc4ae33914db94e8cbd
Source dataset
uspto-grants-2015_03
Patent number
US08987268B2

Reaction notes

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