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
• City of the host institution: São Carlos

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

(17)

(The scientific publications listed on this page originate from the Web of Science or SciELO databases. Their authors have cited FAPESP grant or fellowship project numbers awarded to Principal Investigators or Fellowship Recipients, whether or not they are among the authors. This information is collected automatically and retrieved directly from those bibliometric databases.)

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)

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)

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)

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)

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 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)

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)

MORA VARGAS, JORGE ANDRES; RIBEIRO DA SILVA, JESSICA; LANCAROVICI ALVES, ANA CLARA; GOMEZ HIGUITA, GERMAN DARIO; CARVALHO, ANTONIO JOSE FELIX; BURTOLOSO, ANTONIO C. B.. Novel Sulfur-Containing Polyurethanes using 5-(Chloromethyl)Furfural as a Renewable Building Block. CHEMSUSCHEM, v. N/A, p. 10-pg., 2025-08-07. (21/06549-0, 20/15230-5, 23/08708-4, 20/07147-0)

ALVES, ANA CLARA LANCAROVICI; SANTOS, CAMILA SOUZA; BURTOLOSO, ANTONIO CARLOS BENDER; CARVALHO, ANTONIO JOSE FELIX. Thermoplastic Chitosan Plasticized with Deep Eutectic Solvent Derived from Gamma-valerolactone. JOURNAL OF POLYMERS AND THE ENVIRONMENT, v. 32, n. 11, p. 13-pg., 2024-07-05. (17/23329-9, 20/07147-0)

PEDRO DE F. LIMA, JOAO; GALLO, RAFAEL D. C.; BURTOLOSO, ANTONIO C. B.. α,β-Unsaturated Diazoketones as Building Blocks to Piperidine Alkaloids: Total Synthesis of (-)-Cassine. Journal of Organic Chemistry, v. 90, n. 24, p. 9-pg., 2025-06-10. (20/07147-0, 23/02675-7)

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)

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)

VARGAS, JORGE ANDRES MORA; MANDREKAR, KETAN S.; ECHEMENDIA, RADELL; BURTOLOSO, ANTONIO C. B.. Innovations in isocyanate synthesis for a sustainable future. ORGANIC & BIOMOLECULAR CHEMISTRY, v. N/A, p. 19-pg., 2024-11-11. (20/15230-5, 19/12300-5, 22/09140-9, 20/07147-0, 21/06549-0)

HAYASHI, MARCIO; BURTOLOSO, ANTONIO C. B.. Organocatalytic Transformations from Sulfur Ylides. CATALYSTS, v. 13, n. 4, p. 27-pg., 2023-04-01. (20/07147-0)