Heck-Matsuda Arylation of Alkenyl Ethers and Derivatives: Expansion, Mechanistic Studies and Synthetic Applications of the Redox-Relay Strategy

• Grant number: 16/18061-4
• Support Opportunities: Scholarships in Brazil - Doctorate
• Start date: March 01, 2017
• End date: April 30, 2021
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Organic Chemistry
• Principal Investigator: Carlos Roque Duarte Correia
• Grantee: Henrique Esteves
• Host Institution: Instituto de Química (IQ). Universidade Estadual de Campinas (UNICAMP). Campinas , 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

Remote functionalisation of organic structures has been topic of recent efforts in chemical synthesis. Its versatility allows the achievement of tandem interconversions through distal groups in the molecular backbone. The redox-relay strategy occurring in Heck-Matsuda reaction usually follows the migration of a palladium hydride intermediate through successive migratory insertions along the alkenol carbon chain, consisting in a terminal oxidation process, usually leading an alcohol to the corresponding aldehyde or ketone. This strategy was taken by the scientific community so far as exclusively occurring with free hydroxyl alkenols. Based on anomalous results in our lab whose allowed us to achieve carbonyl products from alkenyl silyl ethers, we proposed the expansion of this protocol to different alkenyl ethers and/or derivatives. This interesting breakthrough raised some mechanistic concerns of redox-relay step which is proposed to be understood by using control experiments, kinetic experiments, isotopic labelling and DFT calculations.

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)

FROTA, CARLISE; POLO, ELLEN CHRISTINE; ESTEVES, HENRIQUE; DUARTE CORREIA, CARLOS ROQUE. Regioselective and Stereoselective Heck Matsuda Arylations of Trisubstituted Allylic Alkenols and Their Silyl and Methyl Ether Derivatives To Access Two Contiguous Stereogenic Centers: Expanding the Redox-Relay Process and Application in the Total Synthesis of meso-Hexestrol. Journal of Organic Chemistry, v. 83, n. 4, p. 2198-2209, FEB 16 2018. (13/10639-9, 14/25770-6, 13/07600-3, 16/18061-4)

Academic Publications

(References retrieved automatically from State of São Paulo Research Institutions)

ESTEVES, Henrique. Mechanistic studies on the oxidative addition of palladium(0) to aryldiazonium cations and on the redox-relay in the Heck-Matsuda reactions of unsaturated ethers. 2021. Doctoral Thesis - Universidade Estadual de Campinas (UNICAMP). Instituto de Química Campinas, SP.