2,2-Diphenyl-5,5-dimethyl-1-oxa-2-silacyclopentane

• 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: 2,2-Diphenyl-5,5-dimethyl-1-oxa-2-silacyclopentane
• 英文别名: 5,5-Dimethyl-2,2-diphenyloxasilolane
• 化学式: C₁₇H₂₀OSi
• 分子量: 268.431
• InChiKey: REULKWYDMXDCHO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.95
• 重原子数：
  19
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  2-甲基-3-丁烯-2-醇 在 铂 四丁基氟化铵 作用下， 以 四氢呋喃 、 正戊烷 为溶剂， 反应 0.5h， 生成 2,2-Diphenyl-5,5-dimethyl-1-oxa-2-silacyclopentane
  参考文献：
  名称：

  Cyclohydrosilylation dimer formation: evidence for Pt0 PtII PtIV catalysis

  摘要：

  An eight-membered cyclic compound, 2,2,3,4,4,6,6,7,8,8-decamethyl-1,5-dioxa-2,4-disilacyclooctane (VIII), along with the expected five-membered 2,2,5,5-tetramethyl-1-oxa-2-silacyclopentane (V) were found to be the major products when vinyldimethylcarbinoxydimethylsilane (1) (i.e. 2-methyl-3-buten-2-oxydimethylsilane) was subjected to cyclohydrosilylation using platinum catalysis. The eight-membered product (VIII) readily undergoes beta-elimination during gas chromatography (GC) analysis to extrude 2-methyl-2-butene giving the six-membered 2,2,4,4,5,6,6-heptamethyl-1,3-dioxa-2,4-disilacyclohexane (VI). Contrary to an earlier report (T.H. Lane and C.L. Frye, J. Organomet. Chem., 172 (1979) 213), no siloxetane or silanone intermediates are needed to rationalize the formation of the six-membered cyclic compound. When (Wilkinson's) rhodium catalyst was used for the hydrosilylation, only V was formed. The formation of VIII with platinum catalysis is rationalized by a mechanism utilizing successive oxidative additions to both Pt0 and Pt(II) catalytic species; i.e. the absence of a second catalytically active level of rhodium is believed responsible for its inability to yield the eight-membered cyclic. Similarly, dimerization of either 1,1-dimethyl-1-silacyclobutane or 1,1,3,3-tetramethyl-1,3-disilacyclobutane to form the cyclooctanes can be readily achieved by platinum catalysis but not by rhodium catalysis. These results constitute the first examples of processes believed to require the presence of not only one but two catalytically active oxidation levels.

  DOI：

  10.1016/0022-328x(93)80051-c

文献信息

• Mechanistic Insights into Grubbs-Type Ruthenium-Complex-Catalyzed Intramolecular Alkene Hydrosilylation: Direct σ-Bond Metathesis in the Initial Stage of Hydrosilylation
  作者：Apparao Bokka、Yuanda Hua、Adam S. Berlin、Junha Jeon

  DOI：10.1021/acscatal.5b00431

  日期：2015.6.5

  synthesis of organosilicon heterocycles from readily available olefins, this study provides fundamental mechanistic insights into the non-metathetical function of Grubbs-type ruthenium catalysts. In the initial stage of hydrosilylation within a ruthenium coordination sphere, evidence for activation of a ruthenium complex by direct σ-bond metathesis between Si–H and Ru–Cl via a four-centered transition state

  已经开发了Grubbs型钌配合物介导的烯基甲硅烷基醚的分子内烯烃氢化硅烷化以提供具有高区域选择性的环状甲硅烷基醚。值得注意的是，这种钌配合物通过非Si-H键活化而不是烯烃活化而非金属地用于烯烃氢化硅烷化反应，在这种情况下，未检测到竞争的烯烃复分解二聚作用。除了从容易获得的烯烃合成有机硅杂环化合物之外，本研究还提供了有关Grubbs型钌催化剂的非复分解功能的基本机理的见解。在钌配位范围内的氢化硅烷化的初始阶段，提出了通过四中心过渡态通过Si–H和Ru–Cl之间的直接σ键复分解来活化钌配合物的证据。3 Si–H穿过Ru-亚苄基的π键。
• Cai, Yudong; Roberts, Brian P., Journal of the Chemical Society. Perkin transactions I, 1998, # 3, p. 467 - 475
  作者：Cai, Yudong、Roberts, Brian P.

  DOI：——

  日期：——
• Cyclohydrosilylation dimer formation: evidence for Pt0 PtII PtIV catalysis
  作者：H.K. Chu、C.L. Frye

  DOI：10.1016/0022-328x(93)80051-c

  日期：1993.3

  An eight-membered cyclic compound, 2,2,3,4,4,6,6,7,8,8-decamethyl-1,5-dioxa-2,4-disilacyclooctane (VIII), along with the expected five-membered 2,2,5,5-tetramethyl-1-oxa-2-silacyclopentane (V) were found to be the major products when vinyldimethylcarbinoxydimethylsilane (1) (i.e. 2-methyl-3-buten-2-oxydimethylsilane) was subjected to cyclohydrosilylation using platinum catalysis. The eight-membered product (VIII) readily undergoes beta-elimination during gas chromatography (GC) analysis to extrude 2-methyl-2-butene giving the six-membered 2,2,4,4,5,6,6-heptamethyl-1,3-dioxa-2,4-disilacyclohexane (VI). Contrary to an earlier report (T.H. Lane and C.L. Frye, J. Organomet. Chem., 172 (1979) 213), no siloxetane or silanone intermediates are needed to rationalize the formation of the six-membered cyclic compound. When (Wilkinson's) rhodium catalyst was used for the hydrosilylation, only V was formed. The formation of VIII with platinum catalysis is rationalized by a mechanism utilizing successive oxidative additions to both Pt0 and Pt(II) catalytic species; i.e. the absence of a second catalytically active level of rhodium is believed responsible for its inability to yield the eight-membered cyclic. Similarly, dimerization of either 1,1-dimethyl-1-silacyclobutane or 1,1,3,3-tetramethyl-1,3-disilacyclobutane to form the cyclooctanes can be readily achieved by platinum catalysis but not by rhodium catalysis. These results constitute the first examples of processes believed to require the presence of not only one but two catalytically active oxidation levels.