Supramolecular Catalysis in water: Probing the influence of a tetrahedral cage on photocyclization and photooxidation.

• Grant number: 15/12305-6
• Support Opportunities: Regular Research Grants
• Duration: October 01, 2015 - September 30, 2017
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Organic Chemistry
• Principal Investigator: Airton Goncalves Salles Junior
• Grantee: Airton Goncalves Salles Junior
• Host Institution: Instituto de Química (IQ). Universidade Estadual de Campinas (UNICAMP). Campinas , SP, Brazil

Abstract

The effect of conformation on reactivity is intimately associated with the details of themechanism of a reaction. A molecule in different conformations may take different reaction pathways thus eroding selectivity in the transformation. Structural modifications and specific reaction conditions are able to drive the transformation towards a unique pathway but such approach is not always doable. Herein we propose the use of a self-assembled supramolecular tetrahedral cage capable of restricting conformational freedom of a guest and favoring one reaction pathway among others. This project is built upon several leading areas of chemistry: Self-assembly of subcomponents; Molecular cages; Supramolecular Catalysis and Green chemistry. We plan to study the following transformations: Selective photocyclization of trans-1,3-pentadiene and related dienes and the photooxidation of enones, both accomplished in water. The enantioselective version of these transformations will be developed using an enantiopure cage described in the case for support. Also, the scope of these reactions will be evaluated. In this way we aim to expand the toolbox of asymmetric catalysis for the synthesis of biologically important molecules and new materials. Collaboration with Prof Nitschke's group will be valuable in order to facilitate the exchange of people of knowledge between Cambridge and Brazil contributing to the academic relevance of the project. (AU)

Scientific publications

(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)

DE SOUZA, GABRIELA F. P.; VON ZUBEN, THEODORA W.; SALLES, JR., AIRTON G.. ``On Water{''} Metal-Catalyst-Free Oxidative Coupling-Amidation of Amines To Access Imines and Amides. ACS SUSTAINABLE CHEMISTRY & ENGINEERING, v. 5, n. 9, p. 8439-8446, SEP 2017. (15/12305-6)

DE SOUZA, GABRIELA F. P.; VON ZUBEN, THEODORA W.; SALLES, AIRTON G., JR.. "On Water" Metal-Catalyst-Free Oxidative Coupling-Amidation of Amines To Access Imines and Amides. ACS SUSTAINABLE CHEMISTRY & ENGINEERING, v. 5, n. 9, p. 8-pg., 2017-09-01. (15/12305-6)