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- Title
Nucleophilic Attack of α-Aminoalkyl Radicals on CarbonNitrogen Triple Bonds to Construct α-Amino Nitriles: An Experimental and Computational Study.
- Authors
Zhang, Chao; Liu, Chunmei; Shao, Ying; Bao, Xiaoguang; Wan, Xiaobing
- Abstract
A new reactivity pattern of α-aminoalkyl radicals, involving nucleophilic attack on CN triple bonds under thermal conditions, has been developed to construct α-amino nitriles. In contrast to previous CH 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 CN bond of PhCOCN followed by an elimination step forms the desired α-aminonitrile and an acyl radical.
- Subjects
NUCLEOPHILIC addition (Chemistry); NITRILES; ORGANIC compounds; METAL catalysts; ACYL radicals
- Publication
Chemistry - A European Journal, 2013, Vol 19, Issue 52, p17917
- ISSN
0947-6539
- Publication type
Article
- DOI
10.1002/chem.201303296