Computational mechanistic studies of transition metal catalyzed functionalizations of alkenes: nonintuitive enantioselectivity induction modes applied on contiguos stereocenter formation and difunctionalizations.

• Grant number: 19/02052-4
• Support Opportunities: Scholarships in Brazil - Post-Doctoral
• Start date: July 01, 2019
• End date: January 14, 2021
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Physical-Chemistry
• Principal Investigator: Ataualpa Albert Carmo Braga
• Grantee: Ricardo Almir Angnes
• Host Institution: Instituto de Química (IQ). Universidade de São Paulo (USP). São Paulo , SP, Brazil
• Associated research grant: 14/25770-6 - New frontiers in cross-coupling reactions promoted by palladium: combining enantioselective catalysis, C-H activations, new materials and in flux reactions aiming at high efficiency and sustainability in synthetic processes, AP.TEM

Abstract

A variety of enantioselective functionalizations of alkenes using palladium oxazoline complexes has been reported in the last few years. The large majority of these processes can have their enantioselectivity rationalized by invoking repulsive steric interactions between the allylic hydrogens of the alkene and a bulky substituent at the oxazoline ligand. However, the origin of the enantioselectivity, in several other cases, could not be rationalized using the aforementioned model. Although these reactions are still regarded as exceptions, the understanding of their enantioselectivity induction mode can lead to a paradigm shift on the development of new alkene functionalization methodologies, with especially intriguing consequences on the creation of contiguous stereocenters and difunctionalizations. This project aims at the computational investigation and rationalization of these enantioselectivity induction modes directly corroborating with the development of new synthetic methodologies.

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)

VIEIRA, CAMILA G.; ANGNES, RICARDO A.; BRAGA, ATAUALPA A. C.; GUSEVSKAYA, V, ELENA; ROSSI, LIANE M.. Palladium-catalyzed sabinene oxidation with hydrogen peroxide: Smart fragrance production and DFT insights. MOLECULAR CATALYSIS, v. 517, JAN 2022. (15/01491-3, 19/02052-4, 14/25770-6)

POLO, ELLEN CHRISTINE; WANG, MARTI FERNANDEZ; ANGNES, RICARDO ALMIR; BRAGA, ATAUALPA A. C.; DUARTE CORREIA, CARLOS ROQUE. Enantioselective Heck Arylation of Acyclic Alkenol Aryl Ethers: Synthetic Applications and DFT Investigation of the Stereoselectivity. ADVANCED SYNTHESIS & CATALYSIS, v. 362, n. 4, DEC 2019. (19/02052-4, 14/25770-6, 13/07600-3, 15/01491-3, 17/21494-2)

BRAGA, INGREDY BASTOS; ANGNES, RICARDO ALMIR; DE LUCCA JUNIOR, EMILIO CARLOS; CARMO BRAGA, ATAUALPA ALBERT; DUARTE CORREIA, CARLOS ROQUE. Enantioselective Synthesis of alpha,beta-Unsaturated Aryl Lactams by Heck-Matsuda and Heck-Mizoroki Arylations of Enelactams. EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, v. 2022, n. 39, p. 7-pg., 2022-07-20. (14/25770-6, 19/02052-4, 13/07600-3, 15/01491-3)