In Tandem Auto-Sustainable Enantioselective Heck-Matsuda Reactions Directly from Anilines

Author(s)

Herrera, Christian Leonardo ; Santiago, Joao Victor ; Pastre, Julio Cezar ; Correia, Carlos Roque Duarte

• Document type: Journal article
• Source: ADVANCED SYNTHESIS & CATALYSIS; v. 364, n. 11, p. 10-pg., 2022-04-22.

Abstract

An in tandem enantioselective Heck-Matsuda (HM) reaction of cyclic and acyclic olefins directly from anilines is described. The method relies on a process involving the progressive in situ diazotization of the starting anilines followed by a palladium-catalyzed Heck-Matsuda arylation using chiral N,N-ligands. This intermolecular enantioselective HM arylation strategy was applied to the desymmetrization of three distinct unactivated olefins as proof of concept. The method demonstrates broad substrate scope furnishing the Heck adducts in good to excellent enantiomeric ratios of up to 99:1, high diastereoselectivities (cyclopenten-3-ol with > 20:1 dr), and good overall yields of up to 82% over 2 or 3 steps. (AU)

• FAPESP's process: 14/26378-2 - Development of methodologies and synthetic processes employing a new technological platform: micro and meso reactor assisted synthesis of natural products and derivatives with potential pharmacological activity
• Grantee: Júlio Cezar Pastre
• Support Opportunities: Research Grants - Young Investigators Grants
• 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
• 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