A ß-Diketiminate-Stabilized Sila-Acyl Chloride: Systematic Access to Base-Stabilized Silicon Analogues of Classical Carbonyl Compounds
A ß-Diketiminate-Stabilized Sila-Acyl Chloride: Systematic Access to Base-Stabilized Silicon Analogues of Classical Carbonyl Compounds
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A-二酮亚胺稳定的硅酰氯：系统获得经典羰基化合物的碱稳定的硅类似物
DOI：
10.1002/ange.201807543
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发表时间：
2018
影响因子：
--
通讯作者：
Do D
中科院分区：
文献类型：
--
作者：
Do D
报道了一种用于合成经典有机羰基化合物的硅类似物的氧化/取代策略，它使用了一种新的β-二酮基二亚胺负载的硅酰氯-这是第一个不使用稳定的路易斯酸分离的此类化合物的例子。SiIV中心的亲核取代反应允许直接获得相应的硅醛和硅酸酯。另一种利用合成步骤相反顺序的方法因相应的具有H或或取代基的SiII系统的简单重排而受挫。因此，(N-nacnac)Si(O)Cl的分离代表着在有机化学中普遍存在的合成方法合成硅酮化合物方面向前迈出的关键一步。
An oxidation/substitution strategy for the synthesis of silicon analogues of classical organic carbonyl compounds is reported, by making use of a novel β‐diketiminate‐supported sila‐acyl chloride—the first example of such a compound isolated without the use of a stabilizing Lewis acid. Nucleophilic substitution at the SiIVcenter allows direct access to the corresponding sila‐aldehyde and sila‐ester. An alternative approach utilizing the reverse order of synthetic steps is thwarted by the facile rearrangement of the corresponding SiIIsystems featuring either H or OR substituents. As such, the isolation of (N‐nacnac)Si(O)Cl represents a key step forward in enabling the synthesis of sila‐carbonyl compounds by a synthetic approach ubiquitous in organic chemistry.