(1S,2S)-2-[1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)ethenyl]-1-(methyldiphenylsilyl)cyclopentane

• 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: (1S,2S)-2-[1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)ethenyl]-1-(methyldiphenylsilyl)cyclopentane
• 英文别名: methyl-diphenyl-[(1S,2S)-2-[1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)ethenyl]cyclopentyl]silane
• 化学式: C₂₆H₃₅BO₂Si
• 分子量: 418.459
• InChiKey: ABTKQBCQUANDPC-ZEQRLZLVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.24
• 重原子数：
  30
• 可旋转键数：
  5
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (1S,2S)-2-[1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)ethenyl]-1-(methyldiphenylsilyl)cyclopentane 在 sodium hydroxide 、 双氧水 作用下， 以 甲醇 为溶剂， 反应 12.0h， 生成 (1S,2S)-2-acetyl-1-(methyldiphenylsilyl)cyclopentane
  参考文献：
  名称：

  Palladium-Catalyzed Asymmetric Silaborative C−C Cleavage of meso-Methylenecyclopropanes

  摘要：

  An enantioselective silaborative C-C cleavage of meso-methylenecyclopropanes (meso-MCPs) was achieved by using a palladium catalyst bearing a chiral monodentate phosphine ligand. The (R)-2-bis(3,5-dimethylphenyl)phosphino-1,1'-binaphthyl gave the highest enantioselectivity in the reactions with (methyldiphenylsilyl)pinacolborane at 50 degrees C, affording derivatives of 2-boryl-4-silyl-1-butene in high yields with high enantiomeric excesses. The reactions of bicyclic MCPs that have fused five- to eight-membered rings gave the corresponding products with 89-91% ee, whereas a little lower ee was observed in the reaction of a non-fused MCP (81% ee). Synthetic applications of the products were demonstrated through synthesis of beta-silyl ketones by H2O2 oxidation and synthesis of stereodefined homoallylic alcohols via homologation-allylboration sequence, in which the chiral beta-substituent of the allylborane has critical impact on the diastereochemical outcome.

  DOI：

  10.1021/ja0703170
• 作为产物：
  描述：

  (1R,5S)-6-methylidenebicyclo[3.1.0]hexane 、 2-(methyldiphenylsilyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 在 bis(dibenzylideneacetone)-palladium⁽⁰⁾ 作用下， 以 甲苯 为溶剂， 生成 (1S,2S)-2-[1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)ethenyl]-1-(methyldiphenylsilyl)cyclopentane
  参考文献：
  名称：

  Palladium-Catalyzed Asymmetric Silaborative C−C Cleavage of meso-Methylenecyclopropanes

  摘要：

  An enantioselective silaborative C-C cleavage of meso-methylenecyclopropanes (meso-MCPs) was achieved by using a palladium catalyst bearing a chiral monodentate phosphine ligand. The (R)-2-bis(3,5-dimethylphenyl)phosphino-1,1'-binaphthyl gave the highest enantioselectivity in the reactions with (methyldiphenylsilyl)pinacolborane at 50 degrees C, affording derivatives of 2-boryl-4-silyl-1-butene in high yields with high enantiomeric excesses. The reactions of bicyclic MCPs that have fused five- to eight-membered rings gave the corresponding products with 89-91% ee, whereas a little lower ee was observed in the reaction of a non-fused MCP (81% ee). Synthetic applications of the products were demonstrated through synthesis of beta-silyl ketones by H2O2 oxidation and synthesis of stereodefined homoallylic alcohols via homologation-allylboration sequence, in which the chiral beta-substituent of the allylborane has critical impact on the diastereochemical outcome.

  DOI：

  10.1021/ja0703170

文献信息

• Palladium-Catalyzed Asymmetric Silaborative C−C Cleavage of <i>meso</i>-Methylenecyclopropanes
  作者：Toshimichi Ohmura、Hiroki Taniguchi、Yoshiyuki Kondo、Michinori Suginome

  DOI：10.1021/ja0703170

  日期：2007.3.1

  An enantioselective silaborative C-C cleavage of meso-methylenecyclopropanes (meso-MCPs) was achieved by using a palladium catalyst bearing a chiral monodentate phosphine ligand. The (R)-2-bis(3,5-dimethylphenyl)phosphino-1,1'-binaphthyl gave the highest enantioselectivity in the reactions with (methyldiphenylsilyl)pinacolborane at 50 degrees C, affording derivatives of 2-boryl-4-silyl-1-butene in high yields with high enantiomeric excesses. The reactions of bicyclic MCPs that have fused five- to eight-membered rings gave the corresponding products with 89-91% ee, whereas a little lower ee was observed in the reaction of a non-fused MCP (81% ee). Synthetic applications of the products were demonstrated through synthesis of beta-silyl ketones by H2O2 oxidation and synthesis of stereodefined homoallylic alcohols via homologation-allylboration sequence, in which the chiral beta-substituent of the allylborane has critical impact on the diastereochemical outcome.