Easily Separable Cyclic Oligosilanes with p‐Methoxyphenyl Groups and Their Stereoselective Functionalization
Easily Separable Cyclic Oligosilanes with p‐Methoxyphenyl Groups and Their Stereoselective Functionalization
复制标题
具有对甲氧基苯基的易分离环状低聚硅烷及其立体选择性官能化
DOI：
10.1002/ejic.202001076
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发表时间：
2021
影响因子：
2.3
通讯作者：
Tokitoh Norihiro
中科院分区：
文献类型：
--
作者：
Omatsu Yamato;Mizuhata Yoshiyuki;Tokitoh Norihiro
合成了一种硅环上分别含有三甲基硅甲基和芳基的新型环状低聚硅烷。具有苯基作为芳基的二氯硅烷的还原缩合得到作为其立体异构体的混合物的五元和六元环状低聚硅烷。另一方面，使用对甲氧基苯基取代苯基导致形成四元和五元环状低聚硅烷，其中每个立体异构体都是可分离的，并在光谱和结构上进行了鉴定。有趣的是，分离的环状五硅烷的脱芳基五氟甲磺酸化从任何立体异构体产生唯一的五氟甲磺酸化的环五硅烷。此外，其进一步氯化、溴化和碘化定量地提供相应的五卤代环五硅烷的唯一立体异构体。
Novel cyclic oligosilanes with trimethylsilylmethyl and aryl groups at each silicon ring atom were synthesized. The reductive condensation of a dichlorosilane having a phenyl group as an aryl group gave five‐ and six‐membered cyclic oligosilanes as mixtures of their stereoisomers. On the other hand, the use ofp‐methoxyphenyl group instead of phenyl group resulted in the formation of four‐ and five‐membered cyclic oligosilanes, from which each stereoisomer was separable and identified spectroscopically and structurally. Interestingly, the dearylative pentatriflation of the isolated cyclic pentasilanes yielded the sole pentatriflated cyclopentasilane from any stereoisomer. In addition, its further chlorination, bromination, and iodination quantitatively afforded the sole stereoisomer of the corresponding pentahalocyclopentasilanes.