Computational and experimental study of catalytic enantioselective visible-light-mediated 6pi-photoelectrocyclization

• Grant number: 24/07892-9
• Support Opportunities: Scholarships in Brazil - Master
• Start date: October 01, 2024
• End date: February 28, 2026
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Organic Chemistry
• Principal Investigator: Ataualpa Albert Carmo Braga
• Grantee: Erick Henrique de Souza Alves
• Host Institution: Instituto de Química (IQ). Universidade de São Paulo (USP). São Paulo , SP, Brazil
• Associated research grant: 22/14310-0 - Linear free energy relationships in asymmetric catalysis, AP.JP
• Associated scholarship(s): 25/00071-2 - Excited State Dynamics on Photosensitizers using the SHARC approach, BE.EP.MS

Abstract

Many natural biological processes involve chiral compounds, in which the opposite enantiomers have a negative or no effect on the linked process. Synthetic chemistry has long sought effective asymmetric synthesis methods, and more recently has considered the environmental impacts that they may have. The 2021 Nobel Prize was awarded for researchers working with asymmetric catalysis (organocatalysis), raising a significant interest in the topic among the global community. Recent investigations have shown that photocatalyzed reactions are an excellent technique to generate chiral compounds. Combined with a special class of ligands, these processes can be visible light driven, making them more economically viable and environmentally friendly. This work seeks to shed light on the effects operating on a recently published 65E catalyzed electrocyclization under performed photochemical conditions and explore catalysts that promote efficient visible-light driven and high enantioselectivity reactions with complementing computational and experimental techniques. This work is expected to reveal insights into its reaction mechanisms and associate the stereodeterming steps with structure-activity relationships of the catalyst steps with catalyst qualities, thereby broadening their applicability.