Stereospecific Palladium‐Catalyzed Acylation of Enantioenriched Alkylcarbastannatranes: A General Alternative to Asymmetric Enolate Reactions. Issue 3 (16th December 2016)

• Record Type: Journal Article
• Authors: Wang, Chao‐Yuan; Ralph, Glenn; Derosa, Joseph; Biscoe, Mark R.
• Is Part Of: Angewandte Chemie international edition. Volume 56:Issue 3(2017)
• Page Start: 856
• Page End: 860
• Publication Date: 2016-12-16
• Subjects: carbastannatrane -- cross coupling -- enolate -- palladium catalysis -- stereospecific catalysis; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201609930
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: We report the development of a Pd‐catalyzed process for the cross coupling of unactivated primary, secondary, and tertiary alkylcarbastannatrane nucleophiles with acyl electrophiles. Reactions involving optically active alkylcarbastannatranes occur with exceptional stereofidelity and with net retention of absolute configuration. Because the stereochemistry of the resulting products is entirely reagent‐controlled, this process may be viewed as a general, alternative approach to the preparation of products typically accessed via asymmetric enolate methodologies. Additionally, we report a new method for the preparation of optically active alkylcarbastannatranes, which should facilitate their future use in stereospecific reactions. Abstract : Finding new ways : A Pd‐catalyzed process for the cross‐coupling of unactivated primary, secondary, and tertiary alkylcarbastannatrane nucleophiles with acyl electrophiles was developed. This reaction provides a general, alternative approach to the preparation of products typically accessed via asymmetric enolate methodologies.