Benzenesulfonyl azide copper catalyzed decomposition

Scheme 12.2 Copper catalyzed decomposition of benzenesulfonyl azide leads to a mixture of C H amination and aziridination products.

Copper-catalyzed decomposition of benzenesulfonyl azide in the presence of cyclohexene was the first reported evidence of a metal-catalyzed nitrene insertion reaction [25]. This seminal discovery was then followed by the pioneering work of Breslow and Gellman who introduced the use of iminoiodinanes as metal nitrene precursors as well as rhodium dimer complexes as catalysts [26,27]. They showed the formation of the corresponding benzosultam in 86% yield in the presence of rhodium (II) acetate dimer (Rh2(OAc)4) via an intramolecular metal nitrene C—H bond insertion reaction (Eq. (5.1)). 

Kwart H, Khan AA. Copper-catalyzed decomposition of benzenesulfonyl azide in cyclohexene solution. J/lm Chem Soc. 1967 89 1951-1953. 

The first metal-catalyzed nitrogen atom-transfer process was reported by Kwart and Khan, who demonstrated that copper powder promoted the decomposition of benzenesulfonyl azide when heated in cyclohexene.280 Evans has demonstrated that Cu(i) and Cu(n) triflate and perchlorate salts are efficient catalysts for the aziridination of olefins employing TsN=IPh as the nitrene precursor.281 Subsequent to this finding, intensive effort has focused on the identification of... 

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