Imidoyl sulfoxonium ylides as new precursors of a-imino metal-carbene complexes in organic synthesis

• Grant number: 20/11955-5
• Support Opportunities: Scholarships abroad - Research Internship - Doctorate
• Start date: January 10, 2021
• End date: January 09, 2022
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Organic Chemistry
• Principal Investigator: Antonio Carlos Bender Burtoloso
• Grantee: Clarice Alves Dale Caiuby
• Supervisor: Christophe Aissa
• Host Institution: Instituto de Química de São Carlos (IQSC). Universidade de São Paulo (USP). São Carlos , SP, Brazil
• Institution abroad: University of Liverpool, England
• Associated to the scholarship: 17/23837-4 - Exploring the application of diazocarbonyl compounds and sulfur ylides in the asymmetric ring opening reactions with epoxides for the synthesis of oxetanes and functionalized alcohols, BP.DR

Abstract

In recent years, sulfur ylides have received significant attention as equivalents of diazo compounds and as precursors of metal-carbene complexes. Although significative advances have been made regarding the use of a-carbonyl metal-carbenes as intermediates in organic synthesis, a less explored type of metal-carbene, containing a-imino group, still have limited sources and few general applications. In this context, our research group envisioned the possibility of using imidoyl sulfoxonium ylides as potential precursors to generate a-imino metal-carbene intermediates. To support our proposal, we recently reported a direct intramolecular C-H functionalization of imidoyl sulfoxonium ylides in the presence of iridium catalyst to provide 2-substituted indoles in a single step. Now, we intend to explore even more the versatility of imidoyl sulfoxonium ylides in classical metal-carbene-mediated transformations to provide functionalized imino products and structural-diverse heterocycles.To this purpose, it is necessary to extend the existing methods in order to achieve other imidoyl sulfoxonium ylides such as the N-alkyl substituted and a-aryl-b-imidoyl substituted ylides. The research group of professor Christophe Aïssa has developed a general protocol for palladium-catalyzed cross-coupling reaction between sulfoxonium ylides and (hetero)aryl bromides or triflates, providing a broader scope of a-aryl-b-carbonyl-sulfoxonium ylides. We intend to use the experience of Prof. Aïssa to achieve a-aryl-b-imidoyl sulfoxonium ylides and apply these new substrates in X-H insertion, C-H functionalization and heretoannulations reactions. (AU)

Scientific publications

(References retrieved automatically from Web of Science and SciELO through information on FAPESP grants and their corresponding numbers as mentioned in the publications by the authors)

CAIUBY, CLARICE A. D.; FURNIEL, LUCAS G.; BURTOLOSO, ANTONIO C. B.. symmetric transformations from sulfoxonium ylide. CHEMICAL SCIENCE, v. 13, n. 5, DEC 2021. (18/17800-3, 20/07147-0, 20/11955-5, 17/23837-4)

CAIUBY, CLARICE A. D.; VIDAL, LUCAS; BURTOLOSO, ANTONIO C. B.; AISSA, CHRISTOPHE. Cyclic Sulfoxonium Ylides: Synthesis and Chemospecific Reactivity in the Catalytic Alkylation of Indoles. CHEMCATCHEM, v. 15, n. 7, p. 6-pg., 2023-03-08. (20/07147-0, 17/23837-4, 20/11955-5)