La désamination nitreuse des aminométhyl-1 phénylsulfonyl-4 cyclohexanols-1 cis et trans

Abstract

Nitrous acid deamination of cis-1-aminomethyl-4-phenylsulfonyl-1-cyclohexanol gives 60% of epoxide and 23% of ring-expanded ketone whereas the trans isomer gives 28% of epoxide and 60% of ring-expanded ketone. The large proportion of epoxide is accounted for by the inductive effect and the field effect of the phenylsulfonyl group; a conformational effect wherein the CH2NH2 group leads to more epoxide when in an equatorial conformation than in an axial is also observed in this reaction. This study required the preparation of 4-phenylthio and 4-phenylsulfonyl cyclohexanols and cis- and trans-1-methyl cyclohexanols.

Use of 2,3-bis(phenylsulfonyl)-1-propene as a multicoupling reagent

“…The major fraction contained 80 mg (90%) of 4-(phenylsulfonyl)cyclohexanone (26), with properties in agreement to those reported in the literature. 35 Reaction of 2,3-Bis(phenylsulfonyl)-l-propene (1) with 1-Pyrrolidino-l-cyclohexene. A solution containing 0.5 g of 1 and 0.24 g of 1-pyrrolidino-l-cyclohexene in 5 mL of absolute…”

“…Stirring 25 with a catalytic amount of pyrrolidine resulted in smooth cyclization to produce the known 4-(phenylsulfonyl)cyclohexanone 26 in 90% yield. 35 The reaction of 1 with the pyrrolidine enamine derived from cyclohexanone was also examined.36 After acidic workup, crystallization from chloroform-hexane gave bicyclo [3.3.1]nonan-9-one 28 in 78% yield.37 Initial nucleophilic attack of the enamine onto 1 produces a zwitterion, which is either neutralized directly by a 1,3-proton shift or indirectly by ejection of phenylsulfinate anion which can act then as a proton acceptor to give a new enamine (i.e. 27).…”