(2R,3R)-1,4-bis[(tert-butyldimethylsilyl)oxy]-2-(methyldiphenylsilyl)-3-[1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)ethenyl]butane | 1384245-87-7

• 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: (2R,3R)-1,4-bis[(tert-butyldimethylsilyl)oxy]-2-(methyldiphenylsilyl)-3-[1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)ethenyl]butane
• 英文别名: tert-butyl-[(2R)-2-[(1R)-2-[tert-butyl(dimethyl)silyl]oxy-1-[methyl(diphenyl)silyl]ethyl]-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)but-3-enoxy]-dimethylsilane
• CAS: 1384245-87-7
• 化学式: C₃₇H₆₃BO₄Si₃
• 分子量: 666.972
• InChiKey: RQOBQDFEIBCFJP-LQJZCPKCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.1
• 重原子数：
  45
• 可旋转键数：
  14
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  36.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (2R,3R)-1,4-bis[(tert-butyldimethylsilyl)oxy]-2-(methyldiphenylsilyl)-3-[1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)ethenyl]butane 在 水 、 双氧水 、 sodium hydroxide 作用下， 以 甲醇 为溶剂， 生成 (3S,4R)-5-((tert-butyldimethylsilyl)oxy)-3-(((tert-butyldimethylsilyl)oxy)methyl)-4-(methyldiphenylsilyl)pentan-2-one
  参考文献：
  名称：

  Enhanced Catalyst Activity and Enantioselectivity with Chirality-Switchable Polymer Ligand PQXphos in Pd-Catalyzed Asymmetric Silaborative Cleavage of meso-Methylenecyclopropanes

  摘要：

  The poly(quinoxaline-2,3-diyl)-based helically chiral phosphine ligands PQXphos exhibited high enantioselectivities up to 97% ee in palladium-catalyzed desymmetrization of meso-1,2-dialkylsubstituted-3-methylenecyclopropanes through silaborative cleavage of the C C bond. The observed enantioselectivities were higher than those obtained with 2-diarylphosphino-1,1'-binaphthyl in our original report. Remarkable rate enhancement was also observed with a series of PQXphos in comparison with the corresponding low-molecular weight ligands.

  DOI：

  10.1021/ja303506k
• 作为产物：
  描述：

  tert-butyl-[[(1S,2R)-2-[[tert-butyl(dimethyl)silyl]oxymethyl]-3-methylidenecyclopropyl]methoxy]-dimethylsilane 、 2-(methyldiphenylsilyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 在 tris-(dibenzylideneacetone)dipalladium(0) 作用下， 以 甲苯 为溶剂， 反应 48.0h， 以62%的产率得到(2R,3R)-1,4-bis[(tert-butyldimethylsilyl)oxy]-2-(methyldiphenylsilyl)-3-[1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)ethenyl]butane
  参考文献：
  名称：

  Enhanced Catalyst Activity and Enantioselectivity with Chirality-Switchable Polymer Ligand PQXphos in Pd-Catalyzed Asymmetric Silaborative Cleavage of meso-Methylenecyclopropanes

  摘要：

  The poly(quinoxaline-2,3-diyl)-based helically chiral phosphine ligands PQXphos exhibited high enantioselectivities up to 97% ee in palladium-catalyzed desymmetrization of meso-1,2-dialkylsubstituted-3-methylenecyclopropanes through silaborative cleavage of the C C bond. The observed enantioselectivities were higher than those obtained with 2-diarylphosphino-1,1'-binaphthyl in our original report. Remarkable rate enhancement was also observed with a series of PQXphos in comparison with the corresponding low-molecular weight ligands.

  DOI：

  10.1021/ja303506k

文献信息

• Enhanced Catalyst Activity and Enantioselectivity with Chirality-Switchable Polymer Ligand PQXphos in Pd-Catalyzed Asymmetric Silaborative Cleavage of <i>meso</i>-Methylenecyclopropanes
  作者：Yuto Akai、Takeshi Yamamoto、Yuuya Nagata、Toshimichi Ohmura、Michinori Suginome

  DOI：10.1021/ja303506k

  日期：2012.7.11

  The poly(quinoxaline-2,3-diyl)-based helically chiral phosphine ligands PQXphos exhibited high enantioselectivities up to 97% ee in palladium-catalyzed desymmetrization of meso-1,2-dialkylsubstituted-3-methylenecyclopropanes through silaborative cleavage of the C C bond. The observed enantioselectivities were higher than those obtained with 2-diarylphosphino-1,1'-binaphthyl in our original report. Remarkable rate enhancement was also observed with a series of PQXphos in comparison with the corresponding low-molecular weight ligands.