New methodological and mechanistic studies related to the Heck arylations employing arenediazonium salts and synthetic applications

• Grant number: 11/23832-6
• Support Opportunities: Regular Research Grants
• Start date: August 01, 2012
• End date: January 31, 2015
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Organic Chemistry
• Principal Investigator: Carlos Roque Duarte Correia
• Grantee: Carlos Roque Duarte Correia
• Host Institution: Instituto de Química (IQ). Universidade Estadual de Campinas (UNICAMP). Campinas , SP, Brazil
• Associated researchers: Caio Costa Oliveira ; Daniela Aline Barancelli ; Francisco de Azambuja ; Roberta Lopes Drekener
• Associated research grant(s): 13/50120-2 - The development of novel gold and palladium-catalyzed transformations involving both redox active and neutral catalyst systems, AP.R

Abstract

The overall research proposal encompass three distinct projects focusing on the methodological, mechanistic, and synthetic aspects of Heck arylations employing arenediazonium salts, the so-called Heck-Matsuda reaction.The first project explores the Heck-Matsuda reaction on substrates which can perform as complexing substrates to the palladium catalyst. This project gives continuity to a well-succeeded project initiated recently in the lab dealing with allylic alcohols. In this new proposal we plan to use substrates such as allylamides, allyl carbamates, allyl malonates and some new allylester derivatives. This type of method is new in the literature - our first publications appearing in 2011 - and demonstrates a high synthetic potential to produce important compound (bioactive compounds, for example) in a regio- and stereocontrolled manner. These are well regarded qualities in a synthetic route.Project 2 deals with the synthesis of new fluorescent probes starting from the Heck-Matsuda reaction. These fluorescent probes constitutes novel compounds and demonstrate an exceptional potential as fluorescent markers of use in Biochemistry and/or Chemical Biology, thus allowing to follow biological processes in a precise way in real time.Project 3 is intended to apply the Heck arylation processes with a more medicinal focus, thus providing new analogues of a family of antitumor compounds known as combretastatins. This new approach to the synthesis of these important compounds poses as an efficient one which can be carried out in a few steps. The more adequate starting material for such an enterprise will be evaluated from dimethyl fumarate and dimethyl acetylenedicarboxylate, and should complement in some way the traditional maleic anhydride used for the first generation of this project. (AU)

Scientific publications

(9)

(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)

ANGNES, RICARDO A.; OLIVEIRA, JULIANA M.; OLIVEIRA, CAIO C.; MARTINS, NELSON C.; CORREIA, CARLOS ROQUE D.. Stereoselective Synthesis of Aryl Cyclopentene Scaffolds by Heck-Matsuda Desymmetrization of 3-Cyclopentenol. CHEMISTRY-A EUROPEAN JOURNAL, v. 20, n. 41, p. 13117-13121, OCT 6 2014. (11/23832-6, 13/07600-3)

PEREZ, CARLA CRISTINA; PENA, JESUS MARCELO; DUARTE CORREIA, CARLOS ROQUE. Improved synthesis of bioactive stilbene derivatives applying design of experiments to the Heck-Matsuda reaction. NEW JOURNAL OF CHEMISTRY, v. 38, n. 8, p. 3933-3938, AUG 2014. (11/23832-6, 12/07461-0)

CANTO, KAREN; RIBEIRO, RODRIGO DA SILVA; BIAJOLI, ANDRE F. P.; CORREIA, CARLOS ROQUE D.. Expeditious Synthesis of the Marine Natural Products Prepolycitrin A and Polycitrins A and B through Heck Arylations. EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, v. 2013, n. 35, p. 8004-8013, DEC 2013. (11/23832-6)

LAUER, MILENA HELMER; DREKENER, ROBERTA LOPES; DUARTE CORREIA, CARLOS ROQUE; GEHLEN, MARCELO HENRIQUE. Fluorescence from bisaryl-substituted maleimide derivatives. PHOTOCHEMICAL & PHOTOBIOLOGICAL SCIENCES, v. 13, n. 6, p. 859-866, 2014. (11/18215-8, 11/08727-1, 10/12193-0, 11/23832-6)

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)

PREDIGER, PATRICIA; DA SILVA, ALLAN RIBEIRO; DUARTE CORREIA, CARLOS ROQUE. Construction of 3-arylpropylamines using Heck arylations. The total synthesis of cinacalcet hydrochloride, alverine, and tolpropamine. Tetrahedron, v. 70, n. 20, p. 3333-3341, MAY 20 2014. (11/23832-6)

CARMONA, RAFAELA C.; CORREIA, CARLOS ROQUE D.. Stereoselective Synthesis of 3-Hydroxy-4-arylcyclopentanones and 4-Arylcyclopentenones through a Heck-Matsuda Desymmetrization of meso cis-4-Cyclopentene-1,3-diol. ADVANCED SYNTHESIS & CATALYSIS, v. 357, n. 12, p. 2639-2643, AUG 24 2015. (11/23832-6, 13/10183-5)

OLIVEIRA, CAIO C.; MARQUES, MARCELO V.; GODOI, MARLA N.; REGIANI, THAIS; SANTOS, VANESSA G.; DOS SANTOS, EMERSON A. F.; EBERLIN, MARCOS N.; SA, MARCUS M.; CORREIA, CARLOS R. D.. Chemo-, Regio- and Stereoselective Heck Arylation of Allylated Malonates: Mechanistic Insights by ESI-MS and Synthetic Application toward 5-Arylmethyl-gamma-lactones. ORGANIC LETTERS, v. 16, n. 19, p. 5180-5183, OCT 3 2014. (11/23832-6, 13/07600-3)

GODOI, MARLA N.; DE AZAMBUJA, FRANCISCO; MARTINEZ, PABLO DAVID G.; MORGON, NELSON H.; SANTOS, VANESSA G.; REGIANI, THAIS; LESAGE, DENIS; DOSSMANN, HELOISE; COLE, RICHARD B.; EBERLIN, MARCOS N.; et al. Revisiting the Intermolecular Fujiwara Hydroarylation of Alkynes. EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, v. 2017, n. 13, p. 1794-1803, APR 3 2017. (10/00257-3, 08/00122-0, 10/11068-7, 11/23832-6)