Estudos iniciais do processo de arilação do canfeno via reação de heck-matsuda

Abstract

The Heck-Matsuda (HM) reaction is a version of the traditional Heck-Mizoroki cross-coupling reaction that makes use of arenediazonium salts as arylating agents under aerobic reaction conditions and without the use of anhydrous solvents. Given the versatility of this class of reactions as a tool for building C-C bonds for the elaboration of products of technological and medicinal interest, we decided to study it as a strategy for derivatization of abundant natural products with the aim of creating chemical libraries of biological interest. For this, we describe here our initial studies on optimization of the reaction conditions of HM arylation of the natural and non-activated olefin known as camphene (1). The results obtained from these efforts

allowed us to achieve an excellent performance of the arylation of camphene (1) using the p- methoxybenzenediazonium tetrafluoroborate salt (2) as an arylating agent and Pd(OAc)2 as a

catalyst for the regio- and stereoselective production of the Heck-Matsuda adduct of interest (3) with E-configuration in yields up to 93%. The HM reaction of camphene (1) as a model compound was successfully optimized on the millimolar scale, and the HM adduct obtained was structurally and stereochemically characterized by 1D and 2D NMR analysis. In conclusion, this work has contributed to expanding the scope of the Heck-Matsuda reaction as a synthetic tool for derivatizing natural products.