Non-Covalent Carbonyl-Directed Heck-Matsuda Desymmetrizations: Synthesis of Cyclopentene-Fused Spirooxindoles, Spirolactones, and Spirolactams

Author(s)

Kattela, Shivashankar ; Heerdt, Gabriel ; Correia, Carlos R. D.

• Document type: Journal article
• Source: ADVANCED SYNTHESIS & CATALYSIS; v. 359, n. 2, p. 260-267, JAN 2017.
• Web of Science Citations: 23

Abstract

Enantioselective carbonyl-directable Heck reactions using aryldiazonium salts were developed with the aim to construct chiral quaternary spiro centers in an efficient manner. Five-and six-membered spirooxindoles, spirolactones, and spirolactams (36 examples) were obtained in good to excellent isolated yields with diastereoselectivities ranging from 13:1 to >20:1, and enantiomeric excesses up to 99% in short reaction times (1.0-1.5 h) under mild conditions (40 degrees C). A rationale for the diastereo- and enantioselectivity based on an unprecedented non-covalent carbonyl group directing effect is also presented, and supported by computational calculations. (AU)

• FAPESP's process: 14/25770-6 - New frontiers in cross-coupling reactions promoted by palladium: combining enantioselective catalysis, C-H activations, new materials and in flux reactions aiming at high efficiency and sustainability in synthetic processes
• Grantee: Carlos Roque Duarte Correia
• Support Opportunities: Research Projects - Thematic Grants
• FAPESP's process: 14/05407-4 - Strategies for the dessymmetrization of cyclopentene scaffolds using the enantioselective Heck-Matsuda reaction and their potential synthetic applications.
• Grantee: Shivashankar Kattela
• Support Opportunities: Scholarships in Brazil - Post-Doctoral
• FAPESP's process: 13/07600-3 - CIBFar - Center for Innovation in Biodiversity and Drug Discovery
• Grantee: Glaucius Oliva
• Support Opportunities: Research Grants - Research, Innovation and Dissemination Centers - RIDC