Catalytic allylic oxidation of internal alkenes to a multifunctional chiral building block

Liela Bayeh, Phong Q. Le, Uttam K. Tambar

Research output: Contribution to journalArticle

18 Citations (Scopus)

Abstract

The stereoselective oxidation of hydrocarbons is one of the most notable advances in synthetic chemistry over the past fifty years. Inspired by nature, enantioselective dihydroxylations, epoxidations and other oxidations of unsaturated hydrocarbons have been developed. More recently, the catalytic enantioselective allylic carbon-hydrogen oxidation of alkenes has streamlined the production of pharmaceuticals, natural products, fine chemicals and other functional materials. Allylic functionalization provides a direct path to chiral building blocks with a newly formed stereocentre from petrochemical feedstocks while preserving the olefin functionality as a handle for further chemical elaboration. Various metal-based catalysts have been discovered for the enantioselective allylic carbon-hydrogen oxidation of simple alkenes with cyclic or terminal double bonds. However, a general and selective allylic oxidation using the more common internal alkenes remains elusive. Here we report the enantioselective, regioselective and E/Z-selective allylic oxidation of unactivated internal alkenes via a catalytic hetero-ene reaction with a chalcogen-based oxidant. Our method enables non-symmetric internal alkenes to be selectively converted into allylic functionalized products with high stereoselectivity and regioselectivity. Stereospecific transformations of the resulting multifunctional chiral building blocks highlight the potential for rapidly converting internal alkenes into a broad range of enantioenriched structures that can be used in the synthesis of complex target molecules.

Original languageEnglish (US)
Pages (from-to)196-200
Number of pages5
JournalNature
Volume547
Issue number7662
DOIs
StatePublished - Jul 13 2017

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Alkenes
Hydrocarbons
Hydrogen
Chalcogens
Carbon
Cycloparaffins
Biological Products
Oxidants
Metals
Pharmaceutical Preparations

ASJC Scopus subject areas

  • Medicine(all)
  • General

Cite this

Catalytic allylic oxidation of internal alkenes to a multifunctional chiral building block. / Bayeh, Liela; Le, Phong Q.; Tambar, Uttam K.

In: Nature, Vol. 547, No. 7662, 13.07.2017, p. 196-200.

Research output: Contribution to journalArticle

Bayeh, Liela ; Le, Phong Q. ; Tambar, Uttam K. / Catalytic allylic oxidation of internal alkenes to a multifunctional chiral building block. In: Nature. 2017 ; Vol. 547, No. 7662. pp. 196-200.
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