Premium
Photolysis of Diazo(pentamethyldisilanyl)methyl Ketones in the Presence of Carbonyl Compounds: Trapping of the Acylsilene Intermediates
Author(s) -
Maas Gerhard,
Alt Mechthild,
Schneider Klaus,
Fronda Antonio
Publication year - 1991
Publication title -
chemische berichte
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 0009-2940
DOI - 10.1002/cber.19911240549
Subject(s) - chemistry , photodissociation , diazo , silylation , cycloaddition , wolff rearrangement , photochemistry , reactive intermediate , medicinal chemistry , ketone , enone , reaction intermediate , organic chemistry , catalysis
UV photolysis of diazo(pentamethyldisilanyl)methyl ketones 1b – d generates acylsilenes (3‐oxo‐1‐sila‐1‐propenes) 3 as reactive intermediates, which can be trapped by enolizable carbonyl compounds in an ene‐type reaction. With non‐enolizable carbonyl compounds or ethyl acetate, they undergo a [4 + 2] cycloaddition. In contrast to the photolysis in the absence of these carbonyl compounds, a Wolff rearrangement of 1b – d (or the derived carbenes) to silyl ketenes 5b – d is observed as a competitive reaction.