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Matrix Isolation and Photochemistry of α‐Diazo Sulfoxides: Formation of α‐Oxo Sulfine as an Intermediate
Author(s) -
Sander Wolfram,
Strehl Anja,
Maguire Anita R.,
Collins Stuart,
Kelleher Patrick G.
Publication year - 2000
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/1099-0690(200010)2000:19<3329::aid-ejoc3329>3.0.co;2-l
Subject(s) - chemistry , matrix isolation , diazo , wolff rearrangement , photochemistry , decane , sulfoxide , medicinal chemistry , infrared spectroscopy , organic chemistry
The photochemistry of the α‐diazo sulfoxides 1a and 1b has been investigated in solid argon at 10 K by IR and UV/Vis spectroscopy. Both diazo compounds react to form sulfine 2a by photochemically induced hetero Wolff rearrangement of sulfinyl carbene 3 , which itself cannot be detected in solid argon. Irradiation at λ > 320 nm results in decomposition of the sulfine 2a to give 2‐oxa‐4‐thiabicyclo[4.4.0]decane‐3.5‐dione ( 5 ) and 7‐oxabicyclo[4.2.0]octan‐8‐one ( 6 ) under abstraction of COS. The matrix‐isolated species have been identified by comparison of experimental and calculated IR spectra.