Premium
1,3‐(C → O) Silyl Shift in α‐Diazo α‐Silyl Ketones: Cycloaddition Reactions and Kinetic Proof for the β‐Siloxydiazoalkene Intermediate
Author(s) -
Munschauer Rainer,
Maas Gerhard
Publication year - 1991
Publication title -
angewandte chemie international edition in english
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 0570-0833
DOI - 10.1002/anie.199103061
Subject(s) - silylation , cycloaddition , diazo , chemistry , isomerization , enol , kinetic energy , silyl ether , medicinal chemistry , enol ether , photochemistry , organic chemistry , catalysis , physics , quantum mechanics
The 1 : 1 cycloadducts 3 and 4 with norbornene and N ‐phenylmaleimide (NPM) , respectively, can be regarded as direct trapping products of the diazoalkenes 2 . A kinetic analysis of the trapping reaction with NPM rules out a [3+2] cycloaddition of the diazoketone 1 with formation of 5 and spontaneous silylketone–silyl enol ether isomerization to 4. The conversion of 1 into 2 already takes place at 25–60°C. R t Bu or p ‐NO 2 C 6 H 4 .