Silicon-based cross-coupling reaction: an environmentally benign version

Abstract

Much attention has been paid to the cross-coupling reaction of organosilicon compounds due to their stability, non-toxicity, and natural abundance of silicon. In addition, the silicon-based cross-coupling has many advantages over other cross-coupling protocols. Successful examples of the silicon-based cross-coupling reaction are reviewed, focusing especially on the advances made in the last decade. Having had a number of highly effective palladium catalysts developed mainly for other cross-coupling reactions, the development of the silicon-based protocol owes heavily to the design of organosilicon reagents which effectively undergo transmetalation, a key elemental step of the silicon-based cross-coupling reaction. This tutorial review thus classifies various organosilicon reagents depending on substituents on silicon and surveys their cross-coupling reactions with various electrophiles.

Catalytic Transformations of Fluorinated Olefins

“…This base-free cross-coupling reaction with arylboronates can be successfully expanded to other fluorinated alkenes (Scheme 23); both vinylidene fluoride and hexafluoropropylene react with 5,5-dimethyl-2-(α-naphthyl)-1,3,2-dioxaborinane in the presence of a Pd(0) catalyst, leading to the corresponding cross-coupling and environmentally benign nature of organosilicon reagents [83][84][85][86][87]. Our group recently developed a novel base-free Hiyama coupling reaction of TFE via its C-F bond activation (Scheme 25) [88].…”

Suzuki–Miyaura and Hiyama coupling catalyzed by PEPPSI-type complexes with non-bulky NHC ligand

“…This is surprising because these two methods, the Suzuki-Miyaura and the Hiyama reactions, present alternative pathways leading to biaryl compounds and, therefore, it could be interesting to estimate their relative applicability under similar reaction conditions. The expected advantages of the Hiyama procedure consist in the low cost, the good availability and stability of the organosilicon reagents, and their environmentally friendly nature [28][29][30]. Moreover, the purification of final biaryls from silicon byproducts can be easier than from organoboron compounds.…”

Trimethylsilyl‐Protected Alkynes as Selective Cross‐Coupling Partners in Titanium‐Catalyzed [2+2+1] Pyrrole Synthesis

“…The TBDMS group provides a more stable silylpyrrole than the TMS group, while the Si(OMe) 3 group provides additional synthetic versatility [11] in Hiyama-type couplings. [12] …”