Enantioselective Synthesis of Chiral Cyclopent‐2‐enones by Nickel‐Catalyzed Desymmetrization of Malonate Esters. Issue 29 (19th June 2018)

• Record Type: Journal Article
• Authors: Karad, Somnath Narayan; Panchal, Heena; Clarke, Christopher; Lewis, William; Lam, Hon Wai
• Is Part Of: Angewandte Chemie international edition. Volume 57:Issue 29(2018)
• Page Start: 9122
• Page End: 9125
• Publication Date: 2018-06-19
• Subjects: asymmetric catalysis -- carbocycles -- cyclization -- isomerization -- nickel; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201805578
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: The enantioselective synthesis of highly functionalized chiral cyclopent‐2‐enones by the reaction of alkynyl malonate esters with arylboronic acids is described. These desymmetrizing arylative cyclizations are catalyzed by a chiral phosphinooxazoline/nickel complex, and cyclization is enabled by the reversible E / Z isomerization of alkenylnickel species. The general methodology is also applicable to the synthesis of 1, 6‐dihydropyridin‐3(2 H )‐ones. Abstract : An E / Z thing : The enantioselective synthesis of highly functionalized chiral cyclopent‐2‐enones by the nickel‐catalyzed desymmetrizating arylative cyclization of alkynyl malonate esters is described. Cyclization is enabled by reversible E / Z isomerization of alkenylnickel species. TFE=2, 2, 2‐trifluoroethanol.