Direct and Enantioselective Aldol Reactions Catalyzed by Chiral Nickel(II) Complexes. Issue 28 (7th June 2021)

• Record Type: Journal Article
• Authors: Kennington, Stuart C. D.; Teloxa, Saul F.; Mellado‐Hidalgo, Miguel; Galeote, Oriol; Puddu, Sabrina; Bellido, Marina; Romea, Pedro; Urpí, Fèlix; Aullón, Gabriel; Font‐Bardia, Mercè
• Is Part Of: Angewandte Chemie international edition. Volume 60:Issue 28(2021)
• Page Start: 15307
• Page End: 15312
• Publication Date: 2021-06-07
• Subjects: aldol reaction -- asymmetric catalysis -- direct reaction -- nickel -- thiazinanethiones; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.202104352
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: A direct and asymmetric aldol reaction of N ‐acyl thiazinanethiones with aromatic aldehydes catalyzed by chiral nickel(II) complexes is reported. The reaction gives the corresponding O ‐TIPS‐protected anti ‐aldol adducts in high yields and with remarkable stereocontrol and atom economy. Furthermore, the straightforward removal of the achiral scaffold provides enantiomerically pure intermediates of synthetic interest, which involve precursors for anti ‐α‐amino‐β‐hydroxy and α, β‐dihydroxy carboxylic derivatives. Theoretical calculations explain the observed high stereocontrol. Abstract : Appropriate and simultaneous activation of robust and easy to handle [Tol‐BINAP]NiCl2 and aromatic aldehydes with TIPSOTf orchestrates a direct, asymmetric, and catalytic aldol reaction of a wide array of N ‐acyl‐1, 3‐thiazinane‐2‐thiones. This method enables the corresponding TIPS‐protected anti aldol adducts to be obtained in a highly efficient and atom economical manner.