Molecular Iodine Mediated Oxidation of Arylated alpha-Carbonyl Sulfoxonium Ylides to 1,2-Dicarbonyl-Containing Compounds

Author(s)

Echemendia, Radell ; De Jesus, Matheus P. ; Furniel, Lucas G. ; Day, David Philip ; Burtoloso, Antonio C. B.

• Document type: Journal article
• Source: EUROPEAN JOURNAL OF ORGANIC CHEMISTRY; v. 2022, n. 26, p. 7-pg., 2022-07-14.

Abstract

Sulfoxonium ylides in recent years have proved to be versatile building blocks and have found applications in the synthesis of structurally diverse organic molecules. In this work, we report a new oxidative, molecular iodine-mediated transformation on sterically encumbered arylated sulfoxonium ylides, which give access to 1,2-dicarbonyl containing compounds. Twenty-six examples have been realized (47-92 % yields), with structural diversity modified at two key sites on the sulfoxonium ylide reactants. Furthermore, the protocol benefits from the use of inexpensive molecular iodine to mediate the oxidation and, from a sustainability viewpoint, short reaction times (30 minutes), ambient temperature, and ethyl acetate as a greener reaction solvent. Experimental studies also gave insight to the mechanism of the reaction, involving DMSO as an oxygen source. (AU)

• FAPESP's process: 18/17800-3 - New methodologies using sulfur ylides for the enantioselective alpha-Heterofunctionalization of carbonyl compounds
• Grantee: Lucas Giani Furniel
• Support Opportunities: Scholarships in Brazil - Doctorate (Direct)
• FAPESP's process: 19/12300-5 - Synthesis of butenolides and butyrolactams from sulfur ylides and diazocompounds
• Grantee: Radell Echemendía Pérez
• Support Opportunities: Scholarships in Brazil - Post-Doctoral
• FAPESP's process: 20/07143-5 - Studies aiming the preparation of pro-chiral ²-ceto sulfoxônios -ketosulfoxonium ylides and their applications in the synthesis of isoquinoline derivatives
• Grantee: Matheus Pereira de Jesus
• Support Opportunities: Scholarships in Brazil - Doctorate (Direct)
• FAPESP's process: 20/07147-0 - Enantioselective alpha-heterofunctionalization of carbonyl compounds using sulfoxonium ylides
• Grantee: Antonio Carlos Bender Burtoloso
• Support Opportunities: Regular Research Grants
• FAPESP's process: 19/05002-8 - Exploration of Enantioselective Transformations of Diazoketones and Sulfoxonium Ylides
• Grantee: David Philip Day
• Support Opportunities: Scholarships in Brazil - Post-Doctoral