2016
DOI: 10.1002/ajoc.201600472
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Highly Chemoselective DMPU‐Mediated Trialkylsilylation of Terminal Alkynes Using Trifluoromethyltrialkylsilane

Abstract: A chemoselective silylation of terminal alkynes with trifluoromethyltrialkylsilane in 1,3‐dimethyl‐3,4,5,6‐tetrahydro‐2(1H)‐pyrimidinone (DMPU) is described. This process is effective even under mild conditions without the use of fluorides or an N‐heterocyclic carbene (NHC), providing a widely applicable method for the synthesis of alkynylsilicon compounds. Moreover, it was found that the preferential deprotonation of terminal alkynes using this system proceeded faster than the trifluoromethylation of aldehyde… Show more

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Cited by 12 publications
(4 citation statements)
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“…The plausible mechanism of the catalyst‐free, solvent‐promoted trifluoromethylation can be explained by assuming the pathway pictured in Scheme . The nitogen or oxygen atoms of NMP would interact with Me 3 Si‐CF 3 ( 2 a ) to give pentacoordinate organosilicon intermediate A ,. Next, insertion of the carbonyl compounds 1 into the Si‐CF 3 bond in the intermediate A might provide the alkoxy intermediates B .…”
Section: Methodsmentioning
confidence: 99%
“…The plausible mechanism of the catalyst‐free, solvent‐promoted trifluoromethylation can be explained by assuming the pathway pictured in Scheme . The nitogen or oxygen atoms of NMP would interact with Me 3 Si‐CF 3 ( 2 a ) to give pentacoordinate organosilicon intermediate A ,. Next, insertion of the carbonyl compounds 1 into the Si‐CF 3 bond in the intermediate A might provide the alkoxy intermediates B .…”
Section: Methodsmentioning
confidence: 99%
“…This marked the first instance of sp C−H silylation with TMSCF 3 in catalyst‐free manner (Figure 41). [164] Besides DMPU, both DMI (1,3‐dimethyl‐2‐imidazolidinone) and DMSO (dimethyl sulfoxide) also activates CF 3 SiMe 3 , albeit resulting in a lower yield of the desired product.…”
Section: Synthesis Of 1‐silyl‐1‐alkynesmentioning
confidence: 99%
“…1.2 构筑 C(sp 2 )-Si 键 2016 年侯召民等 [27] 报道了苯胺衍生物的 C(4)位 C(sp 2 )-H 硅基化反应(Scheme 9A). 该反应适用于多种 类型的硅烷, 且通常对金属试剂敏感的氯硅烷、如苯基 图式 8 叔胺的连续硅基化反应 Scheme 8 Consecutive silylation of tertiary amines 张越涛等 [28] 于 2017 年报道了 B(C 6 在 C(sp 2 )-Si 键构筑方面, 张越涛等 [29] 也报道了非 硼路易斯酸催化的硅基化反应, 实现了 [28] , 2015 年, Grubbs 和 Stoltz 等 [33] 报道了叔丁醇钾催化 与此同时, Kondo 等 [38] 使用 1,3-二甲基-3,4,5,6-四 氢-2(1H)-嘧啶酮(DMPU)作为溶剂和碱, 使用三氟甲基 三 烷 基 硅 烷 为 硅 源 , 实 现 了 芳 基 乙 炔 的 硅 化 反 应 (Scheme 20A). 该方法对芳基的取代基具有较好的兼容 性.…”
Section: 原硅基化反应 该方法可将喹啉中的吡啶环还原为哌啶unclassified