Asymmetric Grignard Synthesis of Tertiary Alcohols through Rational Ligand Design. Issue 15 (20th March 2017)

• Record Type: Journal Article
• Authors: Bieszczad, Bartosz; Gilheany, Declan G.
• Is Part Of: Angewandte Chemie international edition. Volume 56:Issue 15(2017)
• Page Start: 4272
• Page End: 4276
• Publication Date: 2017-03-20
• Subjects: asymmetric synthesis -- Grignard synthesis -- tertiary alcohols -- tridentate ligands -- vitamin E; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201610462
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: A simple, general and practical method is reported for highly enantioselective construction of tertiary alcohols through the direct addition of organomagnesium reagents to ketones. Discovered by rational ligand design based on a mechanistic hypothesis, it has an unprecedented broad scope. It utilizes a new type of chiral tridentate diamine/phenol ligand that is easily removed from the reaction mixture. It is exemplified by application to a formal asymmetric synthesis (>95:5 d.r.) of vitamin E. Abstract : The road less traveled : A simple, general, direct route for asymmetric Grignard synthesis of tertiary alcohols was facilitated by coordinating tridentate ligands to magnesium. The method was found by rational design and has wide scope; it was applied to a formal asymmetric synthesis of vitamin E.