Copper-Catalyzed Umpolung of Imines through Carbon-to-Nitrogen Boryl Migration

We report a general strategy for the catalytic umpolung of imines, which was enabled by an unprecedented 1,2-boryl carbon-to-nitrogen migration. Based on the discovery of a rearrangement of an α-borylalkylamido copper intermediate to an α-borylaminoalkyl copper species through 1,2-migration of a bor...

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Bibliographic Details
Published inACS catalysis Vol. 9; no. 5; pp. 4388 - 4393
Main Authors Li, Zhenghua, Zhang, Liang, Nishiura, Masayoshi, Hou, Zhaomin
Format Journal Article
LanguageEnglish
Published American Chemical Society 03.05.2019
Subjects
copper catalysis
amine synthesis
imine umpolung
allylation
boryl migration
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Summary:We report a general strategy for the catalytic umpolung of imines, which was enabled by an unprecedented 1,2-boryl carbon-to-nitrogen migration. Based on the discovery of a rearrangement of an α-borylalkylamido copper intermediate to an α-borylaminoalkyl copper species through 1,2-migration of a boryl group from carbon to nitrogen and copper migration from nitrogen to carbon, we have developed a copper-catalyzed selective allylation of a wide range of aldimines and ketimines with allyl electrophiles in the presence of B2(pin)2 and LiOtBu. We expect this catalytic imine-umpolung strategy may derive useful methodologies for the synthesis of various functionalized amines.
ISSN:2155-5435
2155-5435
DOI:10.1021/acscatal.9b00777