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Direct Conversion of Nitriles into Alkene "Isonitriles".

ABSTRACT: The sequenced addition of RLi to nitriles, trapping with isopropylformate, and dehydration with phosphoryl chloride provides an efficient, direct synthesis of alkene isocyanides. The one-pot sequence involves a series of carefully orchestrated steps: addition, formylation, tautomerization, and dehydration, with CuCN catalyzing a key equilibration of a formyl imine to an N-formyl enamine. The resulting aromatic alkeneisocyanides, that are otherwise challenging to synthesize, engage in an unusual [4+2]-type cycloaddition/1,3-H shift/decyanation sequence to afford substituted naphthalenes.

SUBMITTER: Li Y

PROVIDER: S-EPMC5176577 | biostudies-literature | 2016 Nov

REPOSITORIES: biostudies-literature

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Direct Conversion of Nitriles into Alkene "Isonitriles".

Li Yajun Y Fleming Fraser F FF

Angewandte Chemie (International ed. in English) 20161025 47

The sequenced addition of RLi to nitriles, trapping with isopropylformate, and dehydration with phosphoryl chloride provides an efficient, direct synthesis of alkene isocyanides. The one-pot sequence involves a series of carefully orchestrated steps: addition, formylation, tautomerization, and dehydration, with CuCN catalyzing a key equilibration of a formyl imine to an N-formyl enamine. The resulting aromatic alkeneisocyanides, that are otherwise challenging to synthesize, engage in an unusual ...[more]

PMID: 27778438

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