1,2-Thio group migration in Rh(II) carbene reactions.
[reaction: see text] A series of beta-thio group substituted alpha-diazo carbonyl compounds have been prepared by nucleophilic substitution reactions of thiophenol, thionaphthol, or benzyl mercaptan with beta-acetoxy-alpha-diazo carbonyl compounds. The diazo decomposition of these diazo carbonyl compounds with various transition metal catalysts, including Rh(II) carboxylates and Cu(I) and Cu(II) complexes, has been investigated. It was found that the diazo decomposition of these compounds gave 1,2-thio group migration products. No 1,2-hydride or 1,2-aryl migration products were observed in all cases.
Xu
Feng
F
Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing 100871, China.
Shi
Weifeng
W
Wang
Jianbo
J