title: Mechanism of the rhodium(iii)-catalyzed alkenylation reaction of N-phenoxyacetamide with styrene or N-tosylhydrazone: a computational study.
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.
authors.affiliation: Department of Chemistry, Jinan University, Huangpu Road West 601, Guangzhou, Guangdong 510632, P. R. China. tchjli@jnu.edu.cn tliaoxj@jnu.edu.cn.
authors.forename: Zhiping
authors.initials: Z
authors.lastname: Qiu
authors.affiliation: Department of Chemistry, Jinan University, Huangpu Road West 601, Guangzhou, Guangdong 510632, P. R. China. tchjli@jnu.edu.cn tliaoxj@jnu.edu.cn.
authors.forename: Jiaojiao
authors.initials: J
authors.lastname: Deng
authors.affiliation: Department of Chemistry, Jinan University, Huangpu Road West 601, Guangzhou, Guangdong 510632, P. R. China. tchjli@jnu.edu.cn tliaoxj@jnu.edu.cn.
authors.forename: Zhongchao
authors.initials: Z
authors.lastname: Zhang
authors.affiliation: Department of Chemistry, Jinan University, Huangpu Road West 601, Guangzhou, Guangdong 510632, P. R. China. tchjli@jnu.edu.cn tliaoxj@jnu.edu.cn.
authors.forename: Caihong
authors.initials: C
authors.lastname: Wu
authors.affiliation: Department of Chemistry, Jinan University, Huangpu Road West 601, Guangzhou, Guangdong 510632, P. R. China. tchjli@jnu.edu.cn tliaoxj@jnu.edu.cn.
authors.forename: Juan
authors.initials: J
authors.lastname: Li
authors.affiliation: Department of Chemistry, Jinan University, Huangpu Road West 601, Guangzhou, Guangdong 510632, P. R. China. tchjli@jnu.edu.cn tliaoxj@jnu.edu.cn.
authors.forename: Xiaojian
authors.initials: X
authors.lastname: Liao