Rhodium(III)‐Catalyzed C—H Vinylation of Arenes: Access to Functionalized Styrenes

Abstract

An effective method has been developed for Rh(III)‐catalyzed direct vinylation of arenes to give functionalized styrenes, using vinyltriethoxysilane as a convenient and inexpensive vinyl source. A wide variety of substrates, including 1‐aryl‐2‐pyrrolidinones, anilines, benzamides and ketones, were compatible with this reaction. Moreover, this method can be applied to the two‐step synthesis of functionalized indoles. Mechanistic investigation reveals that the reaction probably proceeds through an oxidative Heck/desilylation pathway.

Synergistic Dinuclear Rhodium Induced Rhodium-Walking Enabling Alkene Terminal Arylation: A Theoretical Study

“…Rhodium is one of the most common transition metals used in modern homogeneous catalysis and is frequently applied to C­(aryl)–H bond activation and functionalization reactions that enable the introduction of diverse functional groups . Considerable experimental efforts have been devoted to developing rhodium-catalyzed C–H functionalization of substrates including alkanes, arenes, aldehydes, and other alkyl and aryl C–H sources. Recently, researchers have investigated the mechanism of rhodium catalysis .…”

Thioamide‐Directed Transition‐Metal‐Catalyzed C(sp2)−H Vinylation and Arylation of Ferrocenes

“…On the basis of these experimental observations and literature precedents, [20] a possible reaction mechanism was Hiyama cross‐coupling, as shown in Scheme 6. First, Ferrocenothiamide go through a reversible C−H activation to form rhodacycle A , this is followed by a transmetallation pathway promoted by nucleophilic attack of silicon by fluoride anions to form the Cp*Rh(III)‐vinyl intermediate B .…”

“…On the basis of these experimental observations and literature precedents, [20] a possible reaction mechanism was Hiyama cross-coupling, as shown in Scheme 6. In summary, we have developed the Cp* Rh(III)/ Cp*Ir(III) catalyzed CÀ H vinylation/arylation of ferrocenethioamides by using vinyl trimethoxysilane and trimethoxy phenyl silane as vinylation/arylation reagents.…”

Merging C–H Vinylation with Switchable 6π-Electrocyclizations for Divergent Heterocycle Synthesis

“…C−H Vinylation: Development and Scope. Although several directed o-C−H vinylation methodologies have been reported using ethylene gas, 20 vinyl acetate, 21 vinyl stannane, 22 acrylic acid, 23 or vinylsilane, 24 a solution with high monovinylation selectivity, broad substrate scope, and mild reaction conditions remains elusive. Suzuki−Miyaura coupling 25 has been widely used in organic synthesis and the pharmaceutical industry due to its mild reaction conditions, broad substrate scope, and thousands of readily available organoboronic acids.…”