Sander, W,Strehl, A,Maguire, AR,Collins, S,Kelleher, PG;

2000

September

European Journal of Organic Chemistry

Matrix isolation and photochemistry of alpha-diazo sulfoxides: Formation of alpha-oxo sulfine as an intermediate

Validated

()

matrix isolation photochemistry diazo compounds sulfines STABILIZED PHOSPHORUS YLIDES FLASH VACUUM PYROLYSIS CEPHALOSPORINS CARBAPENEMS REACTIVITY GENERATION GEOMETRY

3329

3335

The photochemistry of the alpha-diazo sulfoxides la and Ib 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 lambda > 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.