Brønsted acid and Pd–PHOX dual-catalysed enantioselective addition of activated C-pronucleophiles to internal dienes. Issue 19 (26th April 2019)

• Record Type: Journal Article
• Authors: Park, Sangjune; Adamson, Nathan J.; Malcolmson, Steven J.
• Is Part Of: Chemical science. Volume 10:Issue 19(2019)
• Page Start: 5176
• Page End: 5182
• Publication Date: 2019-04-26
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1039/c9sc00633h
• Languages: English
• ISSNs: 2041-6520

Abstract

Abstract : We describe the development of Pd–PHOX-catalysed enantioselective couplings of internal dienes with malononitrile and other activated C-pronucleophiles. Abstract : We describe the development of Pd–PHOX-catalysed enantioselective couplings of internal dienes with malononitrile and other activated C-pronucleophiles. Reactions are dramatically accelerated by the addition of Et3 N·HBAr F 4 as a Brønsted acid co-catalyst, enabling a suite of products bearing a variety of alkyl substituents at the stereogenic carbon to be prepared. A series of mechanism-oriented experiments reveal key aspects of the catalytic cycle and the importance of the non-coordinating BAr F 4 counterion in not only promoting reactions of internal dienes but also additions of previously unreactive nucleophiles towards terminal dienes.