260358-64-3Relevant academic research and scientific papers
Free-radical cyclization of enantiomerically enriched 2-p-tolylthio derivatives of 2-allylcyclohexanones with Mn(III): Asymmetric synthesis of bridged bicyclic ketones and thiochroman-3-ones
Garcia Ruano,Rumbero
, p. 4427 - 4436 (1999)
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. (C) 1999 Published by Elsevier Science Ltd.
