9-Borabicyclo[3.3.1]nonane,9-(1,1-dimethyl-2-phenylsilacyclopent-2-en-3-yl)- | 873955-98-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 金属杂环化合物
• 英文名称: 9-Borabicyclo[3.3.1]nonane,9-(1,1-dimethyl-2-phenylsilacyclopent-2-en-3-yl)-
• CAS: 873955-98-7
• 化学式: C₂₀H₂₉BSi
• 分子量: 308.347
• InChiKey: KRTURAQADJDYGA-HDICACEKSA-N

物化性质

• 沸点：
  139-142 °C(Press: 0.5 Torr)
• 密度：
  0.98±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.23
• 重原子数：
  22.0
• 可旋转键数：
  2.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  9-Borabicyclo[3.3.1]nonane,9-(1,1-dimethyl-2-phenylsilacyclopent-2-en-3-yl)- 在 咪唑 、 iron(III) chloride 作用下， 以 水 、 乙腈 为溶剂， 反应 40.0h， 生成 1,1-dimethyl-5-phenyl-4-(2,3-dihydro-1H-naphtho[1,8-de][1,3,2]-diazaborinyl)-2,3-dihydrosilole
  参考文献：
  名称：

  Catalytic Access to Diastereometrically Pure Four‐ and Five‐Membered Silyl‐Heterocycles Using Transborylation

  摘要：

  Silyl‐heterocycles offer a unique handle to expand and explore chemical space, reactivity, and functionality. The shortage of catalytic methods for the preparation of diverse and functionalized silyl‐heterocycles however limits widespread exploration and exploitation. Herein the borane‐catalyzed intramolecular 1,1‐carboboration of silyl‐alkynes has been developed for the synthesis of 2,3‐dihydrosilolyl and silylcyclobut‐2‐enyl boronic esters. Successful, catalytic carboboration has been achieved on a variety of functionally diverse silyl‐alkynes, using a borane catalyst and transborylation enabled turnover. Mechanistic studies, including 13C‐labelling, computational studies, and single‐turnover experiments, suggest a reaction pathway proceeding by 1,2‐hydroboration, 1,1‐carboboration, and transborylation to release the alkenyl boronic ester product and regenerate the borane catalyst.

  DOI：

  10.1002/anie.202401737
• 作为产物：
  描述：

  dimethyl(phenylethynyl)(vinyl)silane 、 9-borabicyclo[3.3.1]nonane dimer 以 氘代苯 为溶剂， 生成 9-Borabicyclo[3.3.1]nonane,9-(1,1-dimethyl-2-phenylsilacyclopent-2-en-3-yl)-
  参考文献：
  名称：

  Catalytic Access to Diastereometrically Pure Four‐ and Five‐Membered Silyl‐Heterocycles Using Transborylation

  摘要：

  Silyl‐heterocycles offer a unique handle to expand and explore chemical space, reactivity, and functionality. The shortage of catalytic methods for the preparation of diverse and functionalized silyl‐heterocycles however limits widespread exploration and exploitation. Herein the borane‐catalyzed intramolecular 1,1‐carboboration of silyl‐alkynes has been developed for the synthesis of 2,3‐dihydrosilolyl and silylcyclobut‐2‐enyl boronic esters. Successful, catalytic carboboration has been achieved on a variety of functionally diverse silyl‐alkynes, using a borane catalyst and transborylation enabled turnover. Mechanistic studies, including 13C‐labelling, computational studies, and single‐turnover experiments, suggest a reaction pathway proceeding by 1,2‐hydroboration, 1,1‐carboboration, and transborylation to release the alkenyl boronic ester product and regenerate the borane catalyst.

  DOI：

  10.1002/anie.202401737

文献信息

• An efficient route to substituted 1-silacyclopent-2-enes and 1-silacyclohex-2-enes via consecutive 1,2-hydroboration and 1,1-organoboration
  作者：Bernd Wrackmeyer、Oleg L. Tok、Rhett Kempe

  DOI：10.1016/j.ica.2005.03.016

  日期：2005.11

  The reaction of alkyn-1-yl(vinyl)silanes R2Si(C CR1)CH=CH2[R = Me (1), Ph (2); R-1 = Bu-t (a), Ph (b), SiMe3 (c)] with 9-borabicyclo[3.3.1]nonane in a 1:1 ratio affords the 1-silacyclopent-2-ene derivatives 4a-c (R = Me) and 5a-c (R = Ph) as a result of selective intermolecular 1,2-hydroboration. of the vinyl group, followed by intramolecular 1, 1-organoboration of the alkynyl substituent. The analogous reaction sequence converts the alkyn-1-yl(allyl)dimethylsilanes 3a,c into the 1-silacyclohex-2-ene derivatives 7a,c. All reactions were monitored by Si-29 NMR spectroscopy and the structural assignment of the final products was based on multinuclear magnetic resonance data (H-1, B-11, C-13 and Si-29 NMR). The molecular structure of 6a was determined by X-ray analysis. (c) 2005 Elsevier B.V. All rights reserved.