Carbene fragmentation in the bicyclo[3.1.0]hexyl system: disconnecting the trishomocyclopropenyl cation.
[structure: see text] Fragmentation of cis-3-bicyclo[3.1.0]hexyloxychlorocarbene (4) affords cis- and trans-3-bicyclo[3.1.0]hexyl chlorides, cis- and trans-2-bicyclo[3.1.0]hexyl chlorides, and 2-bicylo[3.1.0]hexene. The promiscuity of product formation, taken together with kinetics and labeling studies, suggests that the fragmentation of 4 proceeds via a 3-bicyclo[3.1.0]hexyl cation-chloride ion pair but largely bypasses a trishomocyclopropenyl cation intermediate.
Moss
Robert A
RA
Department of Chemistry and Chemical Biology, Rutgers, The State University of New Jersey, New Brunswick, New Jersey 08903.
Fu
Xiaolin
X