Rhodium‐Catalyzed Enantioselective Reductive Arylation: Convenient Access to 3, 3‐Disubstituted Oxindoles. Issue 39 (14th August 2017)

• Record Type: Journal Article
• Authors: Jang, Young Jin; Larin, Egor M.; Lautens, Mark
• Is Part Of: Angewandte Chemie international edition. Volume 56:Issue 39(2017)
• Page Start: 11927
• Page End: 11930
• Publication Date: 2017-08-14
• Subjects: cyclization -- homogeneous catalysis -- oxindoles -- reductive arylation -- rhodium; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201704922
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: A rhodium‐Josiphos(L*) catalyzed enantioselective intramolecular hydroarylation reaction is described. The reductive cyclization of o ‐bromoaniline‐derived acrylamides provides convenient access to 3, 3‐disubstituted oxindoles in good yields and with excellent enantioselectivity across a range of substrates. We propose that the key cyclization proceeds via a rhodium(III) intermediate. Overall, this method represents an unusual mode of reactivity for rhodium catalysis and is complementary to palladium(0)‐catalyzed α‐arylation methods. Abstract : All systems Ar go : A novel approach for the synthesis of 3, 3‐disubstituted oxindoles was developed using a rhodium‐Josiphos chiral catalyst system. This unusual enantioselective rhodium‐catalyzed reductive arylation, which functions across a range of substrates, serves as an alternative to palladium(0)‐catalyzed α‐arylation and does not require the use of a strong base for enolate formation.