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Lewis Acid/Base Catalyzed [2+2]‐Cycloaddition of Sulfenes and Aldehydes: A Versatile Entry to Chiral Sulfonyl and Sulfinyl Derivatives
Author(s) -
Koch Florian M.,
Peters René
Publication year - 2011
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201003542
Subject(s) - stereocenter , chemistry , nucleophile , sulfonyl , electrophile , reactivity (psychology) , enantioselective synthesis , cycloaddition , organic chemistry , stereochemistry , catalysis , combinatorial chemistry , medicinal chemistry , alkyl , medicine , alternative medicine , pathology
Abstract The first catalytic asymmetric synthesis of β‐sultones is reported. This development has enabled a rapid access to a number of highly enantioenriched biologically interesting sulfonyl and sulfinyl compound classes, which makes use of the inherent ring strain of the four‐membered heterocycles. The products possess either two vicinal stereocenters, such as in β‐hydroxy‐sulfonamides, ‐sulfonates, ‐sulfones, ‐sulfonic acids, ‐sulfinic acids, γ‐sultines, and γ‐sultones or a single stereocenter, such as in α‐branched alkyl or allyl sulfonic acids. This work also represents the first application of sulfene intermediates in asymmetric catalysis. The reactivity of a sulfene normally acting as an electrophile could be reverted by the formation of a nucleophilic zwitterionic sulfene–amine adduct. To achieve a combination of high enantioselectivity and reactivity, cooperative catalytic action of a chiral nucleophilic tertiary amine (the cinchona alkaloid derivative diydroquinine 2,5‐diphenyl‐4,6‐pyrimidinediyl diether ((DHQ) 2 PYR)) and Bi(OTf) 3 or In(OTf) 3 was of primary importance.