Zn(OTf)2/i-Pr2NEt promoted synthesis of tetraalkynylsilanes

Spesivaya, E. S.; Lupanova, Ida A.; Konshina, Dzh. N.; Коншин, В. В.

doi:10.1016/j.tetlet.2020.152713

Cited by 7 publications

(1 citation statement)

References 27 publications

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“…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). On the other hand, we recently reported a catalytic decarboxylation approach for the synthesis of alkynylsilanes (Scheme c). − In the presence of a copper-based catalyst, a silyl alkynoate is decarboxylated to afford the corresponding alkynylsilane.…”

Section: Introductionmentioning

confidence: 99%

Fluoride Ion-Initiated Decarboxylation of Silyl Alkynoates to Alkynylsilanes

et al. 2021

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This communication describes the development of a metal-free catalytic decarboxylation of silyl alkynoates to alkynylsilanes. Treatment of a silyl alkynoate with a catalytic amount of tetrabutylammonium difluorotriphenylsilicate (TBAT) in N , N -dimethylformamide at 150 °C resulted in decarboxylation to give the corresponding alkynylsilane in good to excellent yield (75 → 95%). The TBAT system was applicable to the decarboxylation of sterically demanding silyl alkynoates such as tert -butyldiphenylsilyl 3-phenylpropiolate. Mechanistic studies revealed that the tetrabutylammonium alkynoate derived from TBAT and the silyl alkynoate act as a catalyst for the decarboxylation.

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Section: Introductionmentioning

confidence: 99%

Fluoride Ion-Initiated Decarboxylation of Silyl Alkynoates to Alkynylsilanes

et al. 2021

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Organocalcium Complex‐Catalyzed Dehydrogenative Coupling of Hydrosilanes with Terminal Alkynes

Liu

Cheng

et al. 2021

Eur J Org Chem

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Alkynylsilanes are an important class of organic compounds and dehydrogenative coupling of hydrosilanes with terminal alkynes provides a convenient and simple route to alkynylsilanes. On the other hand, calcium is an abundant, biocompatible, and environmentally friendly element and using organocalcium complexes as catalytic reagents in organic synthesis recently attracted increasing attentions. Here we report an organocalcium complex‐catalyzed dehydrogenative coupling of hydrosilanes with terminal alkynes. With a calcium alkyl complex [LCaCH2SiMe3] (L=[MeC(NDipp)CHC(tBu)NCH2CH2N(Me)CH2CH2NMe2]−, Dipp=2,6‐(iPr)2C6H3) as the catalyst, the reactions of n‐HexSiH3 with terminal alkynes provide trialkynylsilanes and those of Et2SiH2 with terminal alkynes give monoalkynylsilanes efficiently.

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