Trimethyl-(2-methyl-1-methylsulfanyl-propenyloxy)-silane | 77078-44-5

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: Trimethyl-(2-methyl-1-methylsulfanyl-propenyloxy)-silane
• 英文别名: Trimethyl-(2-methyl-1-methylsulfanylprop-1-enoxy)silane
• CAS: 77078-44-5
• 化学式: C₈H₁₈OSSi
• 分子量: 190.382
• InChiKey: PCIKXRLZMVNOQT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.45
• 重原子数：
  11
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  34.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  Trimethyl-(2-methyl-1-methylsulfanyl-propenyloxy)-silane 、 三甲基氯硅烷 在 sodium 作用下， 以 苯 为溶剂， 反应 4.5h， 以81%的产率得到2-Methyl-1-trimethylsilanyl-1-trimethylsilanyloxy-propene
  参考文献：
  名称：

  Conversion of Carbon-Sulfur Linkages into Carbon–Silicon OnesviaReductive Silylation. Preparation of Silyl Enol Ethers of Acyltrimethylsilanes

  摘要：

  在三甲基氯硅烷存在下，用钠或钾钠合金处理可诱导硫代羧酸 S 酯硅基烯醇醚的碳硫键发生还原性裂解，并以高产率制备出相应的酰基三甲基硅烷硅基烯醇醚。

  DOI：

  10.1246/bcsj.53.2634
• 作为产物：
  描述：

  三甲基氯硅烷 、 S-甲基2-甲基硫代丙酸酯 在 lithium diisopropyl amide 作用下， 生成 Trimethyl-(2-methyl-1-methylsulfanyl-propenyloxy)-silane
  参考文献：
  名称：

  Conversion of Carbon-Sulfur Linkages into Carbon–Silicon OnesviaReductive Silylation. Preparation of Silyl Enol Ethers of Acyltrimethylsilanes

  摘要：

  在三甲基氯硅烷存在下，用钠或钾钠合金处理可诱导硫代羧酸 S 酯硅基烯醇醚的碳硫键发生还原性裂解，并以高产率制备出相应的酰基三甲基硅烷硅基烯醇醚。

  DOI：

  10.1246/bcsj.53.2634

文献信息

• Notable Sulfur Atom Effects on the Regio- and Stereoselective Formation of Oxetanes in Paternò−Büchi Photocycloaddition of Aromatic Aldehydes with Silyl O,S-Ketene Acetals
  作者：Manabu Abe、Kiyotada Fujimoto、Masatomo Nojima

  DOI：10.1021/ja993997i

  日期：2000.5.1

  Paterno-Buchi photocycloaddition of silyl O,S-ketene acetals (SKA) 1 and aromatic aldehydes 2 was investigated in detail. The photoreaction of aldehydes 2a-d with beta,beta-dimethyl-O,S-SKA 1a-e has been found to give, regio- (ca. 70/30 to 90/10) and stereoselectively (ca. 70/30 to 90/10), trans-3-siloxyoxetanes 3 independent upon the aldehyde, the substituents SR1 and SiR3, and reaction medium (solvent and salts). The triplet 2-oxatetramethylene 1,4-diradical T-1,4-DR is reasonably proposed as a common intermediate. The regioselectivity is rationalized by (1) the relative stability of 1,4-diradicals and (2) the relative nucleophilicity of sp(2)-carbons in O,S-SKA. The trans-selectivity is explained by the sulfur atom effects in O,S-SKA 1, which control the approach direction of the electrophilic oxygen of triplet n pi* aldehydes to the nucleophilic alkene. The fast ISC process of the triplet 1-alkylthio-1-siloxy-2-oxatetramethylene 1,4-diradical T-1,4-DR in competition with the bond rotation has been proposed. The substrate-dependent formation of 3fb from E- or Z-1f supports the hypothesis. The S-directed regio- and diastereoselectivity are found for the first time in the present study.
• KUWAJINA I.; MORI A.; KATO M., BULL. CHEM. SOC. JAP., 1980, 53, NO 9, 2634-2638
  作者：KUWAJINA I.、 MORI A.、 KATO M.

  DOI：——

  日期：——