Introduction of a 7-aza-6-MeO-indoline auxiliary in Lewis-acid/photoredox cooperative catalysis: highly enantioselective aminomethylation of a,ß-unsaturated amides

Santosh K. Pagire, Naoya Kumagai, Masakatsu Shibasaki

Research output: Contribution to journalArticlepeer-review

6 Citations (Scopus)

Abstract

An efficient cooperative chiral Lewis acid/photoredox catalytic system for engaging highly reactive radicals in highly enantioselective conjugate addition to a,ß-unsaturated carbonyls is highly desirable. Direct photoexcitation of unbound substrates typically induces undesired background pathways for racemic products and remains a formidable challenge to be addressed in the area of enantioselective photocatalysis. Herein, we report a cooperative catalytic system comprising a chiral Cu(i) complex and an Ir(iii) photocatalyst fueled by visible-light irradiation that allows for seamless integration of the catalytic formation of a-amino alkyl radicals and subsequent enantioselective addition to a,ß-unsaturated amides. A 7-aza-6-MeO-indoline attachment on the amide substrates plays a pivotal role in suppressing the undesired pathways, resulting in excellent enantioselectivity and enabling expedited access to valuable ?-aminobutyramides. The indoline amide was readily diversified with full recovery of the azaindoline attachment, highlighting the synthetic utility of this cooperative catalytic system.

Original languageEnglish
Pages (from-to)5168-5174
Number of pages7
JournalChemical Science
Volume11
Issue number20
DOIs
Publication statusPublished - 2020 May 28
Externally publishedYes

ASJC Scopus subject areas

  • Chemistry(all)

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