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Acylsilenes (3‐Oxo‐1‐sila‐1‐propenes) from Acyl(disilanyl)carbenes
Author(s) -
Schneider Klaus,
Daucher Birgit,
Fronda Antonio,
Maas Gerhard
Publication year - 1990
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.19901230326
Subject(s) - chemistry , ketene , wolff rearrangement , diazo , cyclobutene , substituent , photodissociation , ketone , isomerization , medicinal chemistry , cyclopropanation , benzene , reactive intermediate , stereochemistry , photochemistry , organic chemistry , ring (chemistry) , catalysis
UV photolysis of diazo(disilanyl)methyl ketones 2 in benzene generates acyl(disilanyl)carbenes 3 , which rearrange to 3‐OxO‐1‐sila‐1‐propenes 4 . The latter compounds are reactive intermediates which either cyclize to l‐oxa‐2‐sila‐3‐cyclobutenes 5 or form the eight‐membered cyclodimers 6 , depending on the substituent of the acyl function. In a side reaction, isomerization of 4 to disilylketenes 7 takes place in some cases. On the other hand, photolysis of diazo ketone 13 yields both the l‐oxa‐2‐sila‐3‐cyclobutene 5a (via the acylsilene 14) and the adamantyl (trisilanyl)ketene 15 (by Wolff rearrangement).