Catalyst-Controlled Diastereoselective Synthesis of Cyclic Amines via C-H Functionalization

Sailu Munnuri, Adeniyi Michael Adebesin, Mahesh P. Paudyal, Muhammed Yousufuddin, Alfonso Dalipe, John R. Falck

Research output: Contribution to journalArticle

16 Scopus citations

Abstract

Reliable regio- and stereochemical techniques applicable to nonactivated aliphatic systems remain largely elusive due to the challenges of discriminating between multiple, relatively strong sp3 C-H bonds whose chemical behavior often differ only subtly. Nevertheless, approaches that employ directing groups and/or auxiliaries have emerged, but impose practical restrictions, especially in complex molecule synthesis. This report describes a catalyst-controlled regio- and diastereoselective synthesis of N-unprotected pyrrolidines via dirhodium catalyzed intramolecular nitrene insertion into sp3 C-H bonds. The reaction proceeds at rt without external oxidants, nitrene stabilizing groups, or directing functionality. The insights that emerged from the conformational/stereoselectivity relationships (CSR) between catalysts and substrates provide a framework for rational catalyst design that can accommodate a broader range of aliphatic C-H chemistry.

Original languageEnglish (US)
Pages (from-to)18288-18294
Number of pages7
JournalJournal of the American Chemical Society
Volume139
Issue number50
DOIs
StatePublished - Dec 20 2017

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ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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