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[2 + 1] Cycloaddition Reaction of Dialkylthioketenes with Carbenes – Isomerization of the Resulting Alkylidenethiiranes
Author(s) -
Behr Helmut,
Bolte Oliver,
Dräger Gerald,
Ries Monika,
Schaumann Ernst
Publication year - 1996
Publication title -
liebigs annalen
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 0947-3440
DOI - 10.1002/jlac.199619960809
Subject(s) - chemistry , isomerization , cycloaddition , diazo , decomposition , medicinal chemistry , photochemistry , catalysis , stereochemistry , organic chemistry
Carbenes generated by metal‐catalyzed decomposition of diazo compounds 2 undergo a smooth cycloaddition to the CS bond of thioketenes 1 ; products 3 were characterized by spectroscopic means as well as an X‐ray structural investigation of 3b . However, photolytic generation of diphenylcarbene from diphenylketene led to an isomeric alkylidenethiirane 4a in the reaction with di‐ tert ‐butylthioketene ( 1a ). Analogously, alkylidenethiiranes 3a, b, d, g, h could be photoisomerized to isomers 4a, b, d, g, h . The corresponding rearrangement of S ‐oxides 8 afforded isomers 9 .