Synthesis of β-alkyl cyclopentanones in high enantiomeric excess via copper-catalyzed asymmetric conjugate reduction [17]

Journal of the American Chemical Society

Volumn 122, Issue 28, 2000, Pages 6797-6798

  Moritani, Yasunori ^a   Appella, Daniel H ^a   Jurkauskas, Valdas ^a   Buchwald, Stephen L ^a  

^a MASSACHUSETTS INSTITUTE OF TECHNOLOGY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CYCLOPENTANONE DERIVATIVE;

CATALYSIS; ENANTIOMER; LETTER; MOLECULAR INTERACTION; SYNTHESIS; UNITED STATES;

EID: 0034686724     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0009525     Document Type: Letter

References (31)

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25. p-tol-BINAP = 2,2′-bis(di-p-tolylphosphino)-1,1′-binaphthyl, BINAP = 2.2′-bis(diphenylphosphino)-1,1′-binaphthyl, BIPHEMP = 2,2′-bis(diphenylphosphino)-6,6′-dimethyl-1,1′-biphenyl.
26. PMHS from Aldrich has an average molecular weight between 3200 and 17000. and a density of 1.006 g/mL. From these values, 0.06 mL of PMHS/mmol of Si-H was calculated and this value was used to determine the volume of PMHS to add to the reaction so that there was only 1 equiv of Si-H relative to substrate.
27. We are in the process of developing reaction conditions that do not require a drybox by trying to replace CuCl with a copper salt that is less sensitive to air.
28. Isolation of the volatile product in high yield could only be accomplished by Kugelrohr distillation to remove toluene followed by chromatography with ether/pentane (a high vacuum pump could not be used to remove solvents without losing substantial amounts of the product).
29. Cyclopentenones with substituents larger than an isopropyl group on the β-carbon did not react with the catalyst; for instance, 3-tert-butylcyclopentenone could not be reduced. Additionally, at present we are unable to reduce 2,3-disubstituted cyclopentenones.
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