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7752967 
Journal Article 
Synthesis of 3-azabicyclo[3.1.0]hexanes by insertion of cyclopropylmagnesium carbenoids into an intramolecular C-H bond adjacent to a nitrogen atom 
Molinari, G; Kimura, T; Wada, N; Tsuru, T; Sampei, T; Satoh, T 
2015 
1 
Tetrahedron
ISSN: 0040-4020 
Elsevier Ltd 
71 
35 
5952-5958 
English 
WOS:000358973200029 
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 NCH3, NCH2CH3, NCH2Ph, and NCH(CH3)2. Optically active 3-azabicyclo[3.1.0]hexane was successfully synthesized using an S-chiral p-tolylsulfinyl group as a chiral auxiliary. © 2015 Elsevier Ltd. 
1,5-C-H Insertion; Cyclopropylmagnesium carbenoid; 3-Azabicyclo[3.1.0]hexane; 1-Chlorocyclopropyl p-tolyl sulfoxide; Sulfoxide/magnesium exchange; Chiral auxiliary