Skeletal Rearrangement of Cyano-Substituted Iminoisobenzofurans into Alkyl 2‑Cyanobenzoates Catalyzed by B(C6F5)3
journal contributionposted on 2014-10-03, 00:00 authored by Jing Li, Yasuhiro Okuda, Jiaji Zhao, Seiji Mori, Yasushi Nishihara
An efficient method for the direct conversion of cyano-substituted iminoisobenzofurans into their corresponding alkyl 2-cyanobenzoates has been developed. This transformation proceeds via cleavage of C–C, C–O, and C–N bonds in starting iminoisobenzofurans. DFT study revealed that intermediate α-iminonitriles are produced in situ via C–C bond formation between 2-iminium benzoates and a cyanide ion. Generation of isocyanide as the byproduct in a more thermodynamic manner in DFT calculations also supports the experimental results.