Mechanism of the rhodium(iii)-catalyzed alkenylation reaction of N-phenoxyacetamide with styrene or N-tosylhydrazone: a computational study. Issue 19 (18th April 2016)

• Record Type: Journal Article
• Authors: Qiu, Zhiping; Deng, Jiaojiao; Zhang, Zhongchao; Wu, Caihong; Li, Juan; Liao, Xiaojian
• Is Part Of: Dalton transactions. Volume 45:Issue 19(2016)
• Page Start: 8118
• Page End: 8126
• Publication Date: 2016-04-18
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c6dt00093b
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : A systematic density functional theory study has been conducted to examine the mechanisms involved in the rhodium(iii )-catalyzed alkenylation of N -phenoxyacetamide with two different substrates ( i.e., styrene and N -tosylhydrazone). Abstract : A systematic density functional theory study has been conducted to examine the mechanisms involved in the rhodium(iii )-catalyzed alkenylation of N -phenoxyacetamide with two different substrates ( i.e., styrene and N -tosylhydrazone). The density functional theory calculations indicated that the reaction of the N -tosylhydrazone substrate resulted in the formation of a Rh(v )–nitrene intermediate via the cleavage of the O–N bond of N -phenoxyacetamide, whereas the styrene substrate resulted in an Rh(i ) species through consecutive β-H elimination and H migration steps to the internal oxidant. The differences observed between the N -tosylhydrazone and styrene systems were attributed to differences in the reactivity of their Rh(v )–nitrene intermediates. For example, the N -tosylhydrazone formed a five-membered Rh(v )–nitrene intermediate, which was readily reduced to a Rh(iii ) species by tautomerization, whereas this pathway was energetically unfavorable for the styrene substrate.