Asymmetric induction during Yang cyclization of α-oxoamides: The power of a covalently linked chiral auxiliary is enhanced in the crystalline state

Arunkumar Natarajan, Joel T. Mague, V. Ramamurthy

Research output: Contribution to journalArticle

53 Scopus citations

Abstract

γ-Hydrogen abstraction has been revealed to be the primary photoprocess in the crystalline state of α-oxoamides through photochemical and X-ray structural studies. The outstanding ability of a covalent chiral auxiliary in generating asymmetric induction in the photoproduct β-lactam has been established with 10 examples. We have shown that the crystal lattice preorganizes the reactant molecules toward a single diastereomer of the β-lactam and prevents large motions of the 1,4-diradical intermediate that would result in the loss of stereochemical memory. A rare single-crystal-to- single-crystal transformation path of one of the examples investigated establishes the direct correlation between the stereochemistries of the reactant and the product.

Original languageEnglish (US)
Pages (from-to)3568-3576
Number of pages9
JournalJournal of the American Chemical Society
Volume127
Issue number10
DOIs
StatePublished - Mar 16 2005

ASJC Scopus subject areas

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

Fingerprint Dive into the research topics of 'Asymmetric induction during Yang cyclization of α-oxoamides: The power of a covalently linked chiral auxiliary is enhanced in the crystalline state'. Together they form a unique fingerprint.

  • Cite this