Et2Zn-mediated stoichiometric C(sp)-H silylation of 1-alkynes and chlorosilanes

A Novel One‐Step Synthesis of Silicon‐Containing Arylacetylene Resin Catalyzed by Et2Zn with Excellent Processability and Thermal Properties

“…[31] When the amount of Et 2 Zn with 50 % alkynyl concentration of the reactant is used in the reaction process, the reaction can be performed under optimal conditions and the experimental results are consistent with those described in the literature. [32] Experimental and calculation results reveal that diethylzinc first reacts with phenylacetylene to participate in the reaction in different forms of alkynyl zinc intermediates. There are three possible alkynyl zinc intermediates in the reaction process, namely: PhC�CÀ ZnÀ Et, (PhC�C) 2 Zn and PhC�CÀ ZnÀ Cl.…”

“…There are three possible alkynyl zinc intermediates in the reaction process, namely: PhC�CÀ ZnÀ Et, (PhC�C) 2 Zn and PhC�CÀ ZnÀ Cl. [32] Based on the catalytic mechanism of Et 2 Zn, as described in the literature, the proposed mechanism of Et 2 Zn catalyzing the reaction of DEB and DCMS is shown in Scheme 1. Et 2 Zn protonates the alkyne, thereby generating zinc acetylide A, which undergoes electrophilic coupling with DCMS in order to obtain PSA (Path 1).…”

“…[31] Huang et al reported the first example of Et 2 Zn mediated silylation of 1-aklynes and chlorosilanes and mechanistic studies that support Zn alkynilides as intermediates in the reaction. [32] This reaction protocol comprises a practical method for the preparation of alkynylsilanes. It occurred to us that using Et 2 Zn as a catalyst prepared PSA.…”

Fluoride Ion-Initiated Decarboxylation of Silyl Alkynoates to Alkynylsilanes

“…Alkynylsilanes are useful building blocks in organic synthesis . While the nucleophilic substitution of a halosilane with a metal acetylide prepared by deprotonating a terminal alkyne with an organometallic reagent is one of the most common methods for the synthesis of alkynylsilanes (Scheme a), the high nucleophilicity of metal acetylides limits their functional group tolerance, and the coproducts derived from the organometallic reagents are sometimes problematic from the viewpoints of practicality and atom economy. Therefore, the catalytic Si–C cross-coupling of a terminal alkyne with a silicon electrophile has attracted increasing attention, and various silicon electrophiles such as halosilanes, , hydrosilanes, and vinylsilanes are now available for this purpose (Scheme b).…”

Catalytic Decarboxylation of Silyl Alkynoates to Alkynylsilanes

“…Alkynylsilanes are important building blocks used in transition-metal-catalyzed cross-coupling reactions and related transformations . A conventional synthetic approach to an alkynylsilane involves the nucleophilic substitution of a halosilane with a metal acetylide, which is readily generated by the deprotonation of a terminal alkyne with a strong base, such as an alkyllithium or a Grignard reagent (Scheme a) . However, the coproduction of stoichiometric amounts of metal-based wastes and the low functional-group tolerance associated with the highly reactive metal acetylide are sometimes problematic in terms of practicality and sustainability.…”