title: Nucleophilic attack of α-aminoalkyl radicals on carbon-nitrogen triple bonds to construct α-amino nitriles: an experimental and computational study.
abstract: A new reactivity pattern of α-aminoalkyl radicals, involving nucleophilic attack on C≡N triple bonds under thermal conditions, has been developed to construct α-amino nitriles. In contrast to previous C-H functionalization of tertiary amines involving α-aminoalkyl radicals, this methodology does not require the use of photocatalytic conditions or a transition-metal catalyst. Inexpensive and nontoxic phenylacetonitrile was chosen as cyano source for this α-aminonitrile forming reaction. A plausible mechanism is proposed based upon experimental and computational results. An α-aminoalkyl radical intermediate and benzoyl cyanide have been shown to be key intermediates in this green and mild radical process. Nucleophilic attack of the α-aminoalkyl radical on the C≡N bond of PhCOCN followed by an elimination step forms the desired α-aminonitrile and an acyl radical.
authors.affiliation: Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow (Suzhou) University, Suzhou 215123 (P.R. China), Fax: (+86) 512-6588-0334.
authors.forename: Chao
authors.initials: C
authors.lastname: Zhang
authors.forename: Chunmei
authors.initials: C
authors.lastname: Liu
authors.forename: Ying
authors.initials: Y
authors.lastname: Shao
authors.forename: Xiaoguang
authors.initials: X
authors.lastname: Bao
authors.forename: Xiaobing
authors.initials: X
authors.lastname: Wan
keywords: density functional calculations; radical reactions; reaction mechanisms; reactive intermediates; synthetic methods