New methodologies using sulfur ylides for the enantioselective alpha-Heterofunctionalization of carbonyl compounds

• Grant number: 18/17800-3
• Support Opportunities: Scholarships in Brazil - Doctorate (Direct)
• Start date: December 01, 2018
• End date: January 31, 2023
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Organic Chemistry
• Principal Investigator: Antonio Carlos Bender Burtoloso
• Grantee: Lucas Giani Furniel
• 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 aim to develop new methodologies using these ylides for enantioselective ±-heterofunctionalization of carbonyl compounds.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 ±-aminocarbonyl, ±-hydroxy esthers and ±-carbonyl ethers. There are no reports in the literature for this transformation in an asymmetric fashion.As for the asymmetric synthesis of ±-halogenated and ±-sulfenyl carbonyl compounds, will be evaluated S-H insertion, alkylation/halogenation and dehalogenation reactions catalyzed by chiral Lewis acid. Asymmetric version of this methodology is also unprecedented. (AU)

Scientific publications

(5)

(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)

FURNIEL, LUCAS G.; BURTOLOSO, ANTONIO C. B.. Copper-catalyzed N-H insertion reactions from sulfoxonium ylides. Tetrahedron, v. 76, n. 51, SI, DEC 18 2020. (13/18009-4, 17/23329-9, 18/17800-3)

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)

FURNIEL, LUCAS G.; BURTOLOSO, ANTONIO C. B.. Copper-catalyzed N-H insertion reactions from sulfoxonium ylides. Tetrahedron, v. 76, n. 51, p. 10-pg., 2020-12-18. (17/23329-9, 18/17800-3, 13/18009-4)

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)

Academic Publications

(References retrieved automatically from State of São Paulo Research Institutions)

FURNIEL, Lucas Giani. New methodologies using sulfur ylides for the enantioselective α-heterofunctionalization of carbonyl compounds. 2023. Doctoral Thesis - Universidade de São Paulo (USP). Instituto de Química de São Carlos (IQSC/BT) São Carlos.