Abstract
Conventional methods carrying out C(sp2)−C(sp2) bond formations are typically mediated by transition‐metal‐based catalysts. Herein, we conceptualize a complementary avenue to access such bonds by exploiting the potential of electrochemistry in combination with organoboron chemistry. We demonstrate a transition metal catalyst‐free electrocoupling between (hetero)aryls and alkenes through readily available alkenyl‐tri(hetero)aryl borate salts (ATBs) in a stereoconvergent fashion. This unprecedented transformation was investigated theoretically and experimentally and led to a library of functionalized alkenes. The concept was then carried further and applied to the synthesis of the natural product pinosylvin and the derivatization of the steroidal dehydroepiandrosterone (DHEA) scaffold.
Highlights
Despite its young history of only a few decades, the SuzukiMiyaura reaction is one of the most utilized reaction in modern organic chemistry.[1,2] The palladium-catalyzed coupling of boronic acids with organohalides was awarded with the Nobel prize in 2010, a recent study ranks the SuzukiMiyaura coupling as one of the most frequently used reactions (5th place) in medicinal chemistry.[1]
Innate advantages, including the use of inexpensive and reusable electrodes, reaction tuneability and scalability do rely on the modern and cutting-edge work from Baran, but trace back to many other advances in electrochemical synthesis since the pioneering works of Volta and Faraday in the 19th century.[4]
We demonstrated that the formation of “unsymmetrical“ tetraarylborate salts (TABs) salts is enabled by a triple ligand exchange reaction on commercially available organotrifluroborate species employing aryl-Grignard reagents
Summary
Despite its young history of only a few decades, the SuzukiMiyaura reaction is one of the most utilized reaction in modern organic chemistry.[1,2] The palladium-catalyzed coupling of boronic acids with organohalides was awarded with the Nobel prize in 2010, a recent study ranks the SuzukiMiyaura coupling as one of the most frequently used reactions (5th place) in medicinal chemistry.[1] Besides, many other transitionmetal-mediated cross-couplings, namely Stille, Heck, Negishi, Sonogashira, Hiyama and Kumada are likewise powerful tools to forge new C-C bonds.[3] Such indispensable strategies undoubtedly display many advantages and have inspired us to challenge the formation of C-C bonds without the need of the commonly used transition-metal catalysts, breaking new grounds in the field of cross-coupling reactions. We first started our ambitious concept by replacing the catalyst with an electrochemical setup. Innate advantages, including the use of inexpensive and reusable electrodes, reaction tuneability and scalability do rely on the modern and cutting-edge work from Baran, but trace back to many other advances in electrochemical synthesis since the pioneering works of Volta and Faraday in the 19th century.[4]
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