Transition‐Metal‐Free Reaction of Aryltrimethylammonium Iodides with Arylzinc Reagents

Abstract

Reaction of aryltrimethylammonium iodides with arylzinc chlorides in the absence of a transition-metal catalyst to form biaryl compounds was performed under mild conditions. The reaction was suitable for a broad scope of substrates and exhibited good compatibility of functional groups. The Mg ion was demonstrated to markedly promote the reaction.

Base-promoted direct E-selective olefination of organoammonium salts with sulfones toward stilbenes and conjugated 1,3-dienes

“…1 Since the pioneering Ni-catalyzed Kumada type coupling of organoammonium salts reported by Wenkert and co-workers in 1988, 2 the use of organoammonium salts as electrophiles in organic synthesis has attracted considerable attention. Over the past few decades, a great deal of chemical manipulations of organoammonium salts have been developed by MacMillan, 3 Wang, 4 Watson, 5 Uchiyama, 6 Yu, 7 Zhao 8 and others 9 to build various kinds of C–C bonds and C–heteroatom bonds via C–N bond cleavage, which fully demonstrated the diverse reactivity and the synthetic value of organoammonium salts. While there have been many works focusing on the alkylation, arylation or heteroatomization of organoammonium salts, less attention has been paid to their olefination.…”

Transition‐Metal‐Free Approaches to Arylsulfones using Benzylic Ammonium Salts through C−N Bond Cleavage

“…Due to low‐cost and more environmentally friendly, TM‐free reactions are attracting more and more attention in synthesis of pharmaceuticals . However, limited examples include the TM‐free mediated C−N bond cleavage . For example, Uchiyama and Zhang successfully developed a metal‐free approach to constructed various of C−X bonds (Scheme b), which provided efficient approaches to the synthesis of pharmaceuticals or bioactive molecules.…”

“…[8] However, limited examples include the TMfree mediated CÀ N bond cleavage. [9] For example, Uchiyama and Zhang successfully developed a metal-free approach to constructed various of CÀ X bonds (Scheme 1b), [10] which provided efficient approaches to the synthesis of pharmaceuticals or bioactive molecules. Tian and co-works developed an benzyne-activated stereospecific nucleophilic substitution of enantioenriched tertiary benzylic amines, [11] which applied benzylic amines as carbon electrophiles to nucleophilic substitution reactions.…”