1,3‐(C → O) Silyl Shift in α‐Diazo α‐Silyl Ketones: Cycloaddition Reactions and Kinetic Proof for the β‐Siloxydiazoalkene Intermediate | Zendy

Munschauer Rainer | Zendy; Maas Gerhard | Zendy

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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 .

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