Enantioselective alpha-heterofunctionalization of carbonyl compounds using sulfoxonium ylides

• Grant number: 20/07147-0
• Support Opportunities: Regular Research Grants
• Start date: November 01, 2020
• End date: February 28, 2023
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Organic Chemistry
• Principal Investigator: Antonio Carlos Bender Burtoloso
• Grantee: Antonio Carlos Bender Burtoloso
• Host Institution: Instituto de Química de São Carlos (IQSC). Universidade de São Paulo (USP). São Carlos , SP, Brazil

Abstract

Alpha-Heterofunctionalized carbonyl compounds have a wide versatility as synthetic building blocks, due to a variety of transformations that these can participate. However, there are a limited number of asymmetric methodologies to prepare this class of compounds. Therefore, the development of such methodologies is of great importance in the area of organic synthesis. Combining this need with the synthetic potential of sulfur ylides, this project aims to develop new methodologies using these ylides for enantioselective alpha-heterofunctionalization of carbonyl compounds employing metals and organocatalysts. To do so, asymmetric N-H and O-H insertion reactions with acylated sulfur ylides will be evaluated. This strategy would allow the access to alpha-aminocarbonyl, alpha-hydroxy esthers and alpha-carbonyl ethers. There are no reports in the literature for this transformation in an asymmetric fashion. The asymmetric synthesis of alpha-halogenated and alpha-sulfenyl carbonyl compounds will also be evaluated by means of S-H insertion, alkylation/halogenation and dehalogenation reactions. (AU)

Scientific publications

(12)

(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)

DAY, DAVID P.; VARGAS, JORGE A. M.; BURTOLOSO, ANTONIO C. B.. Synthetic Routes Towards the Synthesis of Geminal alpha-Difunctionalized Ketones. CHEMICAL RECORD, FEB 2021. (20/07147-0, 19/05002-8)

MOMO, PATRICIA B.; MIZOBUCHI, EDUARDO F.; ECHEMENDIA, RADELL; BADDELEY, ISABEL; GRAYSON, MATTHEW N.; BURTOLOSO, ANTONIO C. B.. Organocatalytic Enantioselective Sulfa-Michael Additions to alpha,beta-Unsaturated Diazoketones. Journal of Organic Chemistry, v. 87, n. 5, p. 9-pg., 2022-03-04. (19/12300-5, 20/07147-0, 17/23329-9, 18/02920-3, 15/22003-7)

DAY, DAVID P.; VARGAS, JORGE A. M.; BURTOLOSO, ANTONIO C. B.. Synthetic Routes Towards the Synthesis of Geminal alpha-Difunctionalized Ketones. CHEMICAL RECORD, v. 21, n. 10, SI, p. 2837-2854, OCT 2021. (20/07147-0, 19/05002-8)

FURNIEL, LUCAS G.; ECHEMENDIA, RADELL; BURTOLOSO, ANTONIO C. B.. Cooperative copper-squaramide catalysis for the enantioselective N-H insertion reaction with sulfoxonium ylides. CHEMICAL SCIENCE, v. 12, n. 21, p. 7453-7459, JUN 7 2021. (18/17800-3, 20/07147-0, 19/12300-5)

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)

LEVEILLE, ALEXANDRIA N.; ECHEMENDIA, RADELL; MATTSON, ANITA E.; BURTOLOSO, ANTONIO C. B.. nantioselective Indole Insertion Reactions of alpha-Carbonyl Sulfoxonium Ylide. ORGANIC LETTERS, v. 23, n. 24, p. 9446-9450, DEC 17 2021. (20/07147-0, 17/23329-9, 19/12300-5)

ECHEMENDIA, RADELL; DE JESUS, MATHEUS P.; FURNIEL, LUCAS G.; DAY, DAVID PHILIP; BURTOLOSO, ANTONIO C. B.. Molecular Iodine Mediated Oxidation of Arylated alpha-Carbonyl Sulfoxonium Ylides to 1,2-Dicarbonyl-Containing Compounds. EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, v. 2022, n. 26, p. 7-pg., 2022-07-14. (18/17800-3, 19/12300-5, 20/07143-5, 20/07147-0, 19/05002-8)

VARGAS, JORGE ANDRES MORA; BURTOLOSO, ANTONIO C. B.. CO₂-Based Carbamate Synthesis Utilizing Reusable Polymer-Supported DBU. CHEMSUSCHEM, v. N/A, p. 9-pg., 2023-09-27. (21/06549-0, 20/07147-0, 20/15230-5)

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)

DE JESUS, MATHEUS P.; ECHEMENDIA, RADELL; BURTOLOSO, ANTONIO C. B.. The alpha-alkylation of carbonyl sulfoxonium ylides: studies and applications in the synthesis of new sulfur heterocycles. ORGANIC CHEMISTRY FRONTIERS, v. 10, n. 14, p. 8-pg., 2023-06-09. (19/12300-5, 20/07147-0, 20/07143-5)

DAY, DAVID PHILIP; MORA VARGAS, JORGE ANDRES; BENDER BURTOLOSO, ANTONIO CARLOS. Direct Synthesis of alpha-Fluoro-alpha-Triazol-1-yl Ketones from Sulfoxonium Ylides: A One-Pot Approach. Journal of Organic Chemistry, v. 86, n. 17, p. 12427-12435, SEP 3 2021. (20/07147-0, 19/05002-8)

ECHEMENDIA, RADELL; DE OLIVEIRA, KLEBER T.; BURTOLOSO, ANTONIO C. B.. Visible-Light-Promoted Synthesis of 1,3-Dicarbonyl Sulfoxonium Ylides. ORGANIC LETTERS, v. 24, n. 35, p. 5-pg., 2022-08-26. (19/27176-8, 17/23329-9, 20/06874-6, 19/12300-5, 13/07276-1, 20/07147-0)