1356563-84-2

Upstream product

• 791809-35-3 (E)-4-methyl-7-phenylhept-4-en-3-one 
• 1312031-66-5 [(1S,2R,3R)-2-chloro-1-methyl-3-(2-phenylethyl)-2-((R)-p-tolylsulfinyl)cyclopropyl]-propan-1-one 
• 123849-08-1 (-)-(R)-dichloromethyl p-tolyl sulfoxide 

Downstream Products

• 1356563-92-2 (1R,2S,4R,5S,6S)-2-ethyl-1-methyl-6-(2-phenylethyl)-4-phenyl-3-oxabicyclo[3.1.0]hexane 
• 1356563-88-6 1-((R)-{(1R,2S,3R)-2-[(S)-1-(benzyloxy)propyl]-1-chloro-2-methyl-3-(2-phenylethyl)cyclopropyl}sulfinyl)-4-methylbenzene 

Relevant academic research and scientific papers

Synthesis, including asymmetric synthesis, of 3-oxabicyclo[3.1.0]hexanes and bicyclo[3.1.0]hexanes by the 1,5-CH insertion of cyclopropylmagnesium carbenoids as the key reaction

The addition reactions of α,β-unsaturated carbonyl compounds with dichloromethyl p-tolyl sulfoxide in the presence of NaHMDS or LDA resulted in the formation of adducts, 1-chlorocyclopropyl p-tolyl sulfoxides bearing a carbonyl group at the 2-position, in almost quantitative yields. The carbonyl group of the adducts was transformed to various ether groups to give 1-chlorocyclopropyl p-tolyl sulfoxides bearing an ether functional group at the 2-position in short steps. Treatment of these products with i-PrMgCl at low temperature afforded cyclopropylmagnesium carbenoids via the sulfoxide-magnesium exchange reaction. 1,5-Carbon-hydrogen insertion (1,5-CH insertion) reaction of the generated magnesium carbenoid intermediates took place to give 3-oxabicyclo[3.1.0]hexanes or bicyclo[3.1.0]hexanes bearing an ether group at the 4-position in moderate to good yields. When this procedure was carried out starting with enantiopure dichloromethyl p-tolyl sulfoxide, enantiopure 3-oxabicyclo[3.1.0]hexanes were obtained in good overall yields. These procedures provide a good way for the synthesis, including asymmetric synthesis, of multisubstituted 3-oxabicyclo[3.1.0]hexanes and bicyclo[3.1.0]hexanes from α,β-unsaturated carbonyl compounds and dichloromethyl p-tolyl sulfoxide in short steps.