J. García-Ruano, Á. Rumbero
Nov 19, 1999
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Influential Citations
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Citations
Journal
Tetrahedron-asymmetry
Abstract
Abstract Mn(III)-based oxidative intramolecular cyclization of enantiomerically enriched 2-allyl-2-( p -tolylsulfonyl)-cyclohexanone 4 and 2-allyl-2-( p -tolylsulfenyl)cyclohexanone 9 are reported. The observed chemoselectivity (reaction on the allylic double bond yielding bridged bicyclic ketones vs. reaction on the aromatic ring of the p -tolyl group affording thiochroman-3-ones) depends on the sulfur function (sulfone or thioether, respectively), which determines the electronic density of the p -tolyl ring and the conformational preferences of the starting compounds. The nature of the substituent at C-2 is related to the endo / exo selectivity of the cyclization as well as the regioselectivity in the formation of the enones.