Application of the enantioselective Heck-Matsuda reaction for substrate oriented regioselective desymmetrizations

• Grant number: 13/25849-9
• Support Opportunities: Scholarships in Brazil - Doctorate
• Start date: March 01, 2014
• End date: May 31, 2019
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Organic Chemistry
• Principal Investigator: Carlos Roque Duarte Correia
• Grantee: Ricardo Almir Angnes
• Host Institution: Instituto de Química (IQ). Universidade Estadual de Campinas (UNICAMP). Campinas , SP, Brazil
• Associated scholarship(s): 17/01779-2 - Powerful Partners: Ionic Promoters and the Enantioselective Heck-Matsuda Reaction, BE.EP.DR

Abstract

Based upon the recent developments in enantioselective Heck-Matsuda arylations, it is proposed herein the use of a substrate oriented methodology in order to achieve not only enantioselectivity but also regioselectivity at cyclic olefins desymmetrization. To carry out this transformation it is proposed uncommon intermediates such as a (valence saturated) pentacoordinated cationic PdII specie. Experimental conditions must be optimized, and several olefins containing different directing groups shall be synthesized and finally evaluated in the developed methodologyThrough this proposal highly functionalized building blocks as arylated allylic alcohols possessing two stereogenic centers are going to be reachable in a straight manner. Those units are present in a variety of biologically active compounds.

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 OLIVEIRA, JULIANA MANSO; ANGNES, RICARDO ALMIR; KHAN, ISMAT ULLAH; POLO, ELLEN CHRISTINE; HEERDT, GABRIEL; SERVILHA, BRUNO M.; MENEZES DA SILVA, VITOR H.; BRAGA, ATAUALPA A. C.; DUARTE CORREIA, CARLOS ROQUE. Enantioselective, Noncovalent, Substrate-Directable Heck-Matsuda and Oxidative Heck Arylations of Unactivated Five-Membered Carbocyclic Olefins. CHEMISTRY-A EUROPEAN JOURNAL, v. 24, n. 45, p. 11738-11747, AUG 9 2018. (17/18207-1, 13/00544-0, 14/25770-6, 13/07600-3, 15/01491-3, 16/04963-6, 13/25849-9)

ANGNES, RICARDO A.; POTNIS, CHINMAY; LIANG, SHENGZONG; CORREIA, CARLOS ROQUE D.; HAMMOND, GERALD B.. Photoredox-Catalyzed Synthesis of Alkylaryldiazenes: Formal Deformylative C-N Bond Formation with Alkyl Radicals. Journal of Organic Chemistry, v. 85, n. 6, p. 4153-4164, MAR 20 2020. (17/01779-2, 13/25849-9, 14/25770-6)

ANGNES, RICARDO A.; THOMPSON, LEE M.; MASHUTA, MARK S.; CORREIA, CARLOS R. D.; HAMMOND, GERALD B.. Non-Covalent Substrate Directed Enantioselective Heck Desymmetrization of cis-Cyclohex-4-ene-1,2-diol: Synthesis of all cis Chiral 5-Aryl-cyclohex-3-ene-1,2-diols and Mechanistic Investigation. ADVANCED SYNTHESIS & CATALYSIS, v. 360, n. 19, p. 3760-3767, OCT 4 2018. (17/01779-2, 13/25849-9, 14/25770-6)

Academic Publications

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

ANGNES, Ricardo Almir. Enantioselective Heck reactions of endocyclic alkenes: use of attractive non-covalent interactions for the induction of diastereoselectivity. 2019. Doctoral Thesis - Universidade Estadual de Campinas (UNICAMP). Instituto de Química Campinas, SP.