The carbene fragmentation-ring expansion route to bridgehead carbocations.
[reaction: see text]The products, kinetics, and activation parameters were determined for the fragmentation-ring expansions of 1-norbornylmethyloxychlorocarbene (11) and 3-noradamantylmethyloxychlorocarbene (17). Products from 11 (in dichloroethane) included 1-chlorobicyclo[2.2.2]octane (9, 56%) and 1-chlorobicyclo[3.2.1]octane (10, 37%); from 17, we obtained 1-chloroadamantane (15, 68%) and protoadamantyl chloride (16, 28%).
Moss
Robert A
RA
Department of Chemistry and Chemical Biology, Rutgers, The State University of New Jersey, New Brunswick, New Jersey 08903, USA. moss@rutchem.rutgers.edu
Zheng
Fengmei
F
Fedé
Jean-Marie
JM
Sauers
Ronald R
RR