Journal
NATURE
Volume 547, Issue 7662, Pages 196-+Publisher
NATURE PUBLISHING GROUP
DOI: 10.1038/nature22805
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Funding
- W. W. Caruth Jr Endowed Scholarship
- Robert A. Welch Foundation [I-1748]
- National Institutes of Health [R01GM102604]
- National Science Foundation CAREER Award [1150875]
- Sloan Research Fellowship
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1150875] Funding Source: National Science Foundation
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The stereoselective oxidation of hydrocarbons is one of the most notable advances in synthetic chemistry over the past fifty years(1-3). 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(4-7). 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(8-16). 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.
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