Year: 2019
Type: article
Abstract: The enantioselective hydrocyanation of olefins represents a conceptually straightforward approach to prepare enantiomerically enriched nitriles. These, in turn, comprise or are intermediates in the synthesis of many pharmaceuticals and their synthetic derivatives. Herein, we report a cyanide-free dual Pd/CuH-catalyzed protocol for the asymmetric Markovnikov hydrocyanation of vinyl arenes and the anti-Markovnikov hydrocyanation of terminal olefins in which oxazoles function as nitrile equivalents. After an initial hydroarylation process, the oxazole substructure was deconstructed using a [4 + 2]/retro-[4 + 2] sequence to afford the enantioenriched nitrile product under mild reaction conditions.
DOI: 10.1021/jacs.9b10875
Institution: Massachusetts Institute of Technology
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: green
Awards: G1895872528, Enantio- and Regioselective Synthesis of Amides and Sulfonamides by Cu-Catalyzed Hydrofunctionalization of Alkenes, Synthesis of C-Glycosides and a-Aryl Ethers via Metal-Redox Catalysis, Late Transition Metal Catalysts for Organic Synthesis, G6660599008, G9000100211, G9000350156, Metal-Catalyzed Methods for Organic Synthesis
OpenAlex ID: W2986067576