Diazonium salts reactions with hydride

A further valuable tool in organic chemistry is facilitated by isocyanides the deamination reaction. When the standard deamination reaction via a diazonium salt is undesirable (due to a need to avoid acidic conditions), primary amines can be converted by well-known methods into isocyanides, which are reduced using tri-butyltin hydride under Bartorf s conditions (heating for 5 h at 80 °C in toluene). This reaction sequence has been applied as a new route to 1,3-polyols using azetidinone frameworks 1565 as chiral templates [1188]. Dehydration of the formamide 1567 was accomplished with triphosgene to afford the isocyanide 1568, which was reduced efficiently with tris(trimethylsilyl)silane to afford the desired a,y-dialkoxy ester 1569 in 80% yield [1188]. 

The use of ar diazonium salts as oxidants in synthetic coordination diemistry is illustrated in the reactions of metal hydrides with aryldiazonium cations, which give arjddiazene or ar hydrazido oomple> as products. For example, the reactivity of the oobalKD hydride comple> [CoH P(OEt)2Ph 4L towards p-MeC6H4N2BF4 has been studied.33 Instead of insertion or substitution reactions, one-electron oxidation of... 

---