Organocatalytic Enantioselective Decarboxylative Reaction of Malonic Acid Half Thioesters with Cyclic N-Sulfonyl Ketimines by Using N-Heteroarenesulfonyl Cinchona Alkaloid Amides

• Published in: Chemistry : a European journal Vol. 21; no. 10; pp. 3929 - 3932
• Main Authors: Nakamura, Shuichi, Sano, Masahide, Toda, Ayaka, Nakane, Daisuke, Masuda, Hideki
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 02.03.2015; WILEY‐VCH Verlag; Wiley; Wiley Subscription Services, Inc
• Subjects: Alkaloids; Amides; Amides - chemistry; Catalysis; Catalysts; Chemistry; Chemistry, Multidisciplinary; Cinchona Alkaloids - chemistry; Decarboxylation; Enantiomers; enantioselectivity; Imines; Imines - chemistry; Malonates - chemistry; Mannich reaction; Molecular Structure; Nitriles - chemistry; organocatalysis; Physical Sciences; quaternary stereocenters; Science & Technology; Stereoisomerism; Sulfur Compounds - chemistry; Thioesters; enantioselectivity; PRACTICAL SYNTHESIS; C BOND FORMATION; NUCLEOPHILIC-ADDITION; BROAD SCOPE; 3+2 CYCLOADDITION; organocatalysis; quaternary stereocenters; Mannich reaction; CATALYZED ASYMMETRIC ARYLATION; SULTAM AUXILIARIES; SUPERIOR ELECTROPHILES; PALLADIUM PINCER COMPLEXES
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.201406270

The organocatalytic enantioselective decarboxylative Mannich reaction of malonic acid half thioesters (MAHTs) with cyclic N‐sulfonyl ketimines by using N‐heteroarenesulfonyl cinchona alkaloid amides afforded products with high enantioselectivity. Both enantiomers of the products could be obtained by using pseudoenantiomeric chiral catalysts. The reaction proceeds through a nucleophilic addition of the MAHTs to the ketimines prior to decarboxylation. Lose to win: The organocatalytic enantioselective decarboxylative Mannich reaction of malonic acid half thioesters (MAHTs) with cyclic ketimines by using N‐heteroarenesulfonyl cinchona alkaloid amides afforded products with high enantioselectivity (see scheme). Both enantiomers of the products could be obtained by using pseudoenantiomeric chiral catalysts. The reaction proceeds through a nucleophilic addition of the MAHTs to the ketimines prior to decarboxylation.