The conformational bias of aryl, arylsulfonyl geminally substituted tertiary carbon centers: applications in substrate-based stereocontrol

Jeremy P. Scott; Peter R. Mullens; Sarah E. Brewer; Karel M. J. Brands; Jennifer R. Chilenski; Antony J. Davies; Andrew D. Gibb; David R. Lieberman; Steven F. Oliver; Ulf-H. Dolling

doi:10.1039/B601647B

The conformational bias of aryl, arylsulfonyl geminally substituted tertiary carbon centers: applications in substrate-based stereocontrol†

Jeremy P. Scott,*^a Peter R. Mullens,^a Sarah E. Brewer,^a Karel M. J. Brands,^a Jennifer R. Chilenski,^b Antony J. Davies,^a Andrew D. Gibb,^a David R. Lieberman,^a Steven F. Oliver^a and Ulf-H. Dolling^b

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^a Department of Process Research, Merck Sharp & Dohme Research Laboratories, Hertford Road, Hoddesdon, Hertfordshire
E-mail: jeremy_scott@merck.com

^b Department of Process Research, Merck Research Laboratories, P.O. BOX 2000, Rahway, USA

Abstract

Intramolecular nitrile oxide–olefin cycloaddition to form hexahydrobenzisoxazole 14, which engenders a phenylsulfonyl, 2,5-difluorophenyl geminally substituted carbon substructure, proceeds with up to 99% ds. A rationalization of the high level of substrate-based stereo-induction observed in this and related ketone and acrylonitrile metallohydride reductions, supported by single crystal X-ray crystallography, is presented.

Organic & Biomolecular Chemistry

The conformational bias of aryl, arylsulfonyl geminally substituted tertiary carbon centers: applications in substrate-based stereocontrol†

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The conformational bias of aryl, arylsulfonyl geminally substituted tertiary carbon centers: applications in substrate-based stereocontrol

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