Asymmetric Assembly of All‐Carbon Tertiary/Quaternary Nonadjacent Stereocenters through Organocatalytic Conjugate Addition of α‐Cyanoacetates to a Methacrylate Equivalent. Issue 38 (3rd August 2016)

• Record Type: Journal Article
• Authors: Iriarte, Igor; Vera, Silvia; Badiola, Eider; Mielgo, Antonia; Oiarbide, Mikel; García, Jesús M.; Odriozola, José M.; Palomo, Claudio
• Is Part Of: Chemistry. Volume 22:Issue 38(2016)
• Page Start: 13690
• Page End: 13696
• Publication Date: 2016-08-03
• Subjects: asymmetric organocatalysis -- Brønsted bases -- Michael reactions -- quaternary stereocenters -- stereoselective protonation; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201603082
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: An efficient, highly diastereo‐ and enantioselective assembly of acyclic carbonyl fragments possessing nonadjacent all‐carbon tertiary/quaternary stereoarrays is reported based on a Brønsted base catalyzed Michael addition/α‐protonation sequence involving α‐cyanoacetates and 2, 4‐dimethyl‐4‐hydroxypenten‐3‐one as novel methacrylate equivalent. Abstract : Michael does it again ! 2, 4‐Dimethyl‐4‐hydroxypenten‐3‐one has been introduced as new methacrylate equivalent for the asymmetric construction of nonadjacent all carbon tertiary/quaternary stereocenters through the organocatalytic addition of α‐cyanoacetates (see scheme). Direct assembly of such stereoarrays with high enantio‐ and diastereoselectivity has remained elusive to date.