Enantioselective oxy-Heck-Matsuda arylation in styrenic system: enantioselective synthesis of substituted trans-dihydrobenzofuram system and total synthesis of the neolignan (-)-conocarpan

Author(s)

Allan Ribeiro da Silva

• Document type: Doctoral Thesis
• Press: Campinas, SP.
• Institution: Universidade Estadual de Campinas (UNICAMP). Instituto de Química
• Defense date: 2017-12-11

Examining board members

Carlos Roque Duarte Correia; Diogo Seibert Lüdtke; Cristiano Raminelli; Airton Gonçalves Salles Junior; Ronaldo Aloise Pilli

• Advisor: Carlos Roque Duarte Correia

Abstract

The formation of C-C bonds in an enantioselective manner is of crucial importance in organic synthesis. In this regard, the enantioselective Heck¿Matsuda reaction is a very valuable synthetic tool. This arylation reaction has many advantages when compared to other Heck procedures, such as practicality, efficiency and speed. Recently, we developed a new method based on palladium catalysis for the preparation of trans-substituted dihydrobenzofurans in a diastereo and enantioselective way. Using the N,N-chiral ligand PyriBox we develop a method to promote the arylation of styrene using 2-hydroxylated aryldiazonium salt. The corresponding substituted 2,3-dihydrobenzofurans were obtained in yields up to 74% with excellent diastereoselectivity and good enantio control (up to 20:1 dr and 90:10 er). Our protocol was evaluated using diazonium salts containing EDG or EWG groups, several olefins with different substitution patterns. The absolute stereochemistry of the Heck¿Matsuda products were determined by X-ray and the total synthesis of natural product (-)-conocarpan (AU)

• FAPESP's process: 13/25886-1 - Enantioselective Heck-Matsuda reaction involving styrenics systems: trans-dihydrobenzofurans substituted synthesis
• Grantee: Allan Ribeiro da Silva
• Support Opportunities: Scholarships in Brazil - Doctorate