trans-1,1-dimethyl-2-deuterio-3-methoxysilacyclopentane | 141119-04-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: trans-1,1-dimethyl-2-deuterio-3-methoxysilacyclopentane
• CAS: 141119-04-2；141119-10-0
• 化学式: C₇H₁₆OSi
• 分子量: 145.281
• InChiKey: ZLHYAHHBPJLKKV-HCYPKXBVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.11
• 重原子数：
  9.0
• 可旋转键数：
  1.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  9.23
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为产物：
  描述：

  1,1-dimethyl-1-silacyclopent-2-ene 、 氘代甲醇-d 生成 [cyclopropyl(deuterio)methyl]-methoxy-dimethylsilane 、 trans-1,1-dimethyl-2-deuterio-3-methoxysilacyclopentane 、 (Z)-(but-3-en-1-yl-4-d)(methoxy)dimethylsilane 、 (E)-(but-3-en-1-yl-4-d)(methoxy)dimethylsilane
  参考文献：
  名称：

  The far-UV photochemistry of five- and six-membered-ring monosilacycloalkenes in alcohols: stereospecific .beta.-cleavage to silyl ethers and stereoselective formation of silacycloalkyl ethers

  摘要：

  Photoalcoholysis of 1,1-dimethylsilacyclopent-2-ene (9) at 214 nm in methanol, 2,2,2-trifluoroethanol, and tert-butyl alcohol affords alkoxy(3-butenyl)dimethylsilanes 11 and 3-alkoxy-1,1-dimethylsilacyclopentanes 12. Also formed are alkoxy(cyclopropylmethyl)silanes 13 from apparent 1,3-C migration. In pure, deuterated alcohols (CH3OD and CF3CD2OD) adducts It and 12 become trans deuterated, whereas in dilute solutions of methanol-O-d in pentane, scrambling of deuterium between the trans and cis C-2 positions of 12 is observed without corresponding loss of stereospecificity for formation of silyl ether 11. Silyl ether 11 is thus produced via a pathway which is mechanistically distinct from that giving 12, for which the loss of stereoselectivity in dilute alcohols is ascribed to pseudorotational scrambling of deuterium in a silacyclopentyl cation intermediate. At high concentrations of alcohol the trans-stereoselective deuteration of 12 can be attributed to least hindered anti attack of the alcohol at C-3 of this hyperconjugatively stabilized cation. High cis-stereoselective deuteration of 12 is observed for photolysis in dilute CF3CD2OD in pentane, possibly reflecting the intermediacy of an ion pair or unsymmetrically solvated silacyclopentyl cation. Photoalcoholyses of the silacyclohex-2-ene were conducted for comparison.

  DOI：

  10.1021/jo00037a030