O-ATOM INSERTION INTO SI-H BONDS BY DIOXIRANES - A STEREOSPECIFIC AND DIRECT CONVERSION OF SILANES INTO SILANOLS
O-ATOM INSERTION INTO SI-H BONDS BY DIOXIRANES - A STEREOSPECIFIC AND DIRECT CONVERSION OF SILANES INTO SILANOLS
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DOI：
10.1002/anie.199008901
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发表时间：
1990-08-01
期刊：
影响因子：
--
通讯作者：
CURCI, R
中科院分区：
文献类型：
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作者：
ADAM, W;MELLO, R;CURCI, R
硅烷醇在有机硅化学中用作制备有用的”结构单元”的关键中间体。[31此外，近年来，对光学活性硅烷醇的兴趣日益增加，因为它们在实验药理学中被认为是有用的药物，例如硅丙环胺型的光学活性抗毒蕈碱剂。由于通常的合成方法受到副产物如二硅氧烷R、SiOSiR、SiO2、SiO 3等的阻碍，因此似乎非常需要和感兴趣的是开发制备方法以实现硅烷到硅烷醇的直接、立体选择性转化。例如，通过使用过氧苯甲酸，2c到3c的转化可以仅以49%的产率完成; 16]三烷基硅烷的臭氧化反应只得到相应的硅烷醇作为主要产物，通过一个涉及氢三氧化物R3 Si 000 H作为中间体的途径。[*]我们现在报道硅烷2a-c”。10]定量地和立体特异性地转化成相应的硅烷醇3a-3b '-。在低于环境温度下用二氧杂环乙烷1a的溶液处理后[Eq.（一）]。显著数据总结见表1。
Silanols serve as key intermediates in the preparation of useful" building blocks" in organosilicon chemistry.[31 Furthermore, in recent years there has been an increasing interest in optically active silanols, because they figure as useful drugs in experimental pharmacol~ gy,[~ I eg optically active antimuscarinic agents of the sila-procyclidine type. Since the usual synthetic methodologies are encumbered by side products such as disiloxanes R, SiOSiR,,['] there seems to be much need and interest in developing preparative methods to achieve the direct, stereoselective conversion of silanes into silanols.For instance, by using peroxybenzoic acid, the conversion of 2c into 3c could be accomplished in only 49% yield; 16] ozonization of trialkylsilanes ['I afforded the corresponding silanols only as major products, by a pathway involving hydrotrioxides R3Si000H as intermediates.[*] We now report that silanes 2a-c". lo] are quantitatively and stereospecifically converted into the corresponding silanols 3a-~['~.''I upon treatment with solutions of dioxirane 1 a, bat subambient temperatures [Eq.(I)]. Salient data are summarized in Table 1.