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Characteristic Reactions of 4‐Siloxy‐2,5‐dihydrooxepines: Desilylation, [2 + 2] and [4 + 2] Cycloadditions
Author(s) -
Hofmann Bernhard,
Reißig HansUlrich
Publication year - 1994
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.1491271135
Subject(s) - chemistry , bicyclic molecule , tetracyanoethylene , moiety , enol ether , silyl enol ether , reactivity (psychology) , ether , enol , silylation , medicinal chemistry , derivative (finance) , organosilicon , stereochemistry , organic chemistry , catalysis , medicine , alternative medicine , pathology , financial economics , economics
Abstract Desilylation of 4‐siloxy‐2,5‐dihydrooxepine 1 with NEt 3 · HF afforded oxepinone 2. [2 + 2] Cycloadditions of 1 and methyl‐substituted derivative 4 to tetracyanoethylene provided bicyclic products 3 and 5 , respectively. Hetero Diels‐Alder reactions of 2,5‐dihydrooxepines 1 and 9 with 1,1,1‐trifluoro‐2‐nitrosopropene furnished the corresponding bicyclic 1,2‐oxazines 8 and 10 , resp., in reasonable yields. The considerably higher reactivity of the silyl enol ether unit compared with the endocyclic enol ether moiety as revealed by these cycloadditions is discussed.