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

14 Citations (Scopus)

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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Amines
Pyrrolidines
Catalysts
Oxidants
Stereoselectivity
Chemical bonds
Molecules
Substrates
phenylnitrene

ASJC Scopus subject areas

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

Cite this

Catalyst-Controlled Diastereoselective Synthesis of Cyclic Amines via C-H Functionalization. / Munnuri, Sailu; Adebesin, Adeniyi Michael; Paudyal, Mahesh P.; Yousufuddin, Muhammed; Dalipe, Alfonso; Falck, John R.

In: Journal of the American Chemical Society, Vol. 139, No. 50, 20.12.2017, p. 18288-18294.

Research output: Contribution to journalArticle

Munnuri, Sailu ; Adebesin, Adeniyi Michael ; Paudyal, Mahesh P. ; Yousufuddin, Muhammed ; Dalipe, Alfonso ; Falck, John R. / Catalyst-Controlled Diastereoselective Synthesis of Cyclic Amines via C-H Functionalization. In: Journal of the American Chemical Society. 2017 ; Vol. 139, No. 50. pp. 18288-18294.
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