Substrate controlled Heck reactions using arenediazonium salts and the development of the enantioselective version of the Heck-Matsuda reaction.

• Grant number: 13/00544-0
• Support Opportunities: Scholarships in Brazil - Post-Doctoral
• Effective date (Start): August 01, 2013
• Effective date (End): July 31, 2016
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Organic Chemistry
• Principal Investigator: Carlos Roque Duarte Correia
• Grantee: Juliana Manso de Oliveira Silva
• Host Institution: Instituto de Química (IQ). Universidade Estadual de Campinas (UNICAMP). Campinas , SP, Brazil

Abstract

The present proposal is divided into two parts. The first one deals with the Heck-Matsuda reaction directed by the substrate which will be studied on allylic systems to obtain arylated compounds with high regio and stereocontrol. The products obtained in these studies will be applied in a new methodology for the Tsuji-Trost reactions aiming at creating new routes to natural products with potential anticancer activity, as well as in the synthesis of asymmetric cyclopenten derivatives. The second part of the proposal aims at expanding the scope of the enantioselective Heck-Matsuda reaction, recently disclosed by the research group. In this proposal, we plan to synthesize new chiral ligand of the bisoxazoline family and a few other derivatives of those in order to generate in situ chiral palladium catalysts. Additionally, new substrates for the enantioselective Heck-Matsuda reaction will be evaluated. The initial substrates will be bisallylic systems, which will function as potential precursors for enantiomerically enriched aryl lactones. The first experiments will focus on the synthesis of five-membered aryl lactones.

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)

SILVA, JULIANA DE OLIVEIRA; ANGNES, RICARDO A.; MENEZES DA SILVA, VITOR H.; SERVILHA, BRUNO M.; ADEEL, MUHAMMAD; BRAGA, ATAUALPA A. C.; APONICK, AARON; CORREIA, CARLOS ROQUE D.. Intermolecular Noncovalent Hydroxy-Directed Enantioselective Heck Desymmetrization of Cyclopentenol: Computationally Driven Synthesis of Highly Functionalized cis-4-Arylcyclopentenol Scaffolds. Journal of Organic Chemistry, v. 81, n. 5, p. 2010-2018, MAR 4 2016. (13/04813-6, 13/00544-0, 15/01491-3, 11/23832-6, 13/07600-3)

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)