Tsutomu Kimura, Natsumi Wada, Takahiro Tsuru
Sep 2, 2015
Citations
0
Influential Citations
11
Citations
Journal
Tetrahedron
Abstract
Abstract A variety of 3-azabicylo[3.1.0]hexanes were synthesized via 1,5-C–H insertion of cyclopropylmagnesium carbenoids as a key step. 1-Chlorocyclopropyl p -tolyl sulfoxides with an N , N -disubstituted aminomethyl group on the cyclopropane ring were prepared from dichloromethyl p -tolyl sulfoxide, α,β-unsaturated carboxylic acid esters, primary amines, and alkyl halides. Treatment of the sulfoxides with i -PrMgCl generated cyclopropylmagnesium carbenoids, which were inserted into an intramolecular C–H bond adjacent to a nitrogen atom to give 3-azabicyclo[3.1.0]hexanes in yields of up to 94%. The reactivity of the C–H bond toward the insertion increased in the order of NC H 3 , NC H 2 CH 3 , N CH 2 Ph, and NC H (CH 3 ) 2 . Optically active 3-azabicyclo[3.1.0]hexane was successfully synthesized using an S -chiral p -tolylsulfinyl group as a chiral auxiliary.