Asymmetric intramolecular α-cyclopropanation of aldehydes using a donor/acceptor carbene mimetic

Chaosheng Luo, Zhen Wang and Yong Huang ()
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Chaosheng Luo: Key Laboratory of Chemical Genomics, Shenzhen Graduate School, Peking University, Xili University Town
Zhen Wang: Key Laboratory of Chemical Genomics, Shenzhen Graduate School, Peking University, Xili University Town
Yong Huang: Key Laboratory of Chemical Genomics, Shenzhen Graduate School, Peking University, Xili University Town

Nature Communications, 2015, vol. 6, issue 1, 1-11

Abstract: Abstract Enantioselective α-alkylation of carbonyl is considered as one of the most important processes for asymmetric synthesis. Common alkylation agents, that is, alkyl halides, are notorious substrates for both Lewis acids and organocatalysts. Recently, olefins emerged as a benign alkylating species via photo/radical mechanisms. However, examples of enantioselective alkylation of aldehydes/ketones are scarce and direct asymmetric dialkylation remains elusive. Here we report an intramolecular α-cyclopropanation reaction of olefinic aldehydes to form chiral cyclopropane aldehydes. We demonstrate that an α-iodo aldehyde can function as a donor/acceptor carbene equivalent, which engages in a formal [2+1] annulation with a tethered double bond. Privileged bicyclo[3.1.0]hexane-type scaffolds are prepared in good optical purity using a chiral amine. The synthetic utility of the products is demonstrated by versatile transformations of the bridgehead formyl functionality. We expect the concept of using α-iodo iminium as a donor/acceptor carbene surrogate will find wide applications in chemical reaction development.

Date: 2015
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DOI: 10.1038/ncomms10041

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