Organocatalytic Stereoconvergent Synthesis of α‐CF3 Amides: Triketopiperazines and Their Heterocyclic Metamorphosis. Issue 37 (12th June 2017)

• Record Type: Journal Article
• Authors: Foster, Robert W.; Lenz, Eva N.; Simpkins, Nigel S.; Stead, Darren
• Is Part Of: Chemistry. Volume 23:Issue 37(2017)
• Page Start: 8810
• Page End: 8813
• Publication Date: 2017-06-12
• Subjects: organocatalysis -- pyrimidine -- synthetic methods -- trifluoromethyl -- triketopiperazine; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201701548
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: The highly enantioselective alkylation of α‐CF3 enolates, generated from triketopiperazines, has been accomplished through use of a bifunctional thiourea organocatalyst to facilitate 1, 4‐addition to varied enone acceptors. On treatment with appropriate nitrogen nucleophiles, the chiral triketopiperazine products undergo a metamorphosis, to provide novel fused heterocyclic lactams such as extended pyrazolopyrimidines. Abstract : All about that base : The organocatalytic stereoconvergent synthesis of α‐CF3 amides has been developed. This approach has been used to access a diverse range of enantioenriched triketopiperazine products and a novel reaction mechanism has been elucidated. In addition, an enamine‐mediated rearrangement was developed for the regioselective synthesis of enantiopure semi‐saturated pyrazolopyrimidines.