tert-butyl-[[(1S,2R)-2-[[tert-butyl(dimethyl)silyl]oxymethyl]-3-methylidenecyclopropyl]methoxy]-dimethylsilane | 1182218-15-0

• 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: tert-butyl-[[(1S,2R)-2-[[tert-butyl(dimethyl)silyl]oxymethyl]-3-methylidenecyclopropyl]methoxy]-dimethylsilane
• CAS: 1182218-15-0
• 化学式: C₁₈H₃₈O₂Si₂
• 分子量: 342.67
• InChiKey: DMWYCKVGDUHPOL-IYBDPMFKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.83
• 重原子数：
  22
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.89
• 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：

  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

• Nickel-Catalyzed Regio- and Stereoselective Reductive Coupling between Methylenecyclopropanes, Aldehydes, and Triethylborane with Retention of the Cyclopropane Ring
  作者：Kenichi Ogata、Daisuke Shimada、Shin-ichi Fukuzawa

  DOI：10.1002/chem.201200271

  日期：2012.5.14

  Running rings: The first regio‐ and stereoselective reductive coupling between methylenecyclopropanes, aldehydes, and triethylborane with retention of the cyclopropane ring was achieved using a nickel–phosphine catalyst (see scheme). The reductive coupling reaction constructed a stereo‐defined cyclopropane ring with formation of a quaternary stereogenic carbon center.

  运转环：使用镍-膦催化剂（见方案）在亚甲基环丙烷，醛和三乙基硼烷之间保留环丙烷环的第一区域和立体选择性还原偶联。还原偶联反应构建了一个立体定义的环丙烷环，并形成了一个四级立体原子碳中心。
• Nickel-Catalyzed Ring-Opening Alkylative Coupling of Enone with Methylenecyclopropane in the Presence of Triethylborane
  作者：Kenichi Ogata、Daisuke Shimada、Shouichi Furuya、Shin-ichi Fukuzawa

  DOI：10.1021/ol303548x

  日期：2013.3.15

  Nickel-catalyzed alkylative coupling of an enone or enal with methylenecyclopropane in the presence of triethylborane was achieved via stereospecific proximal C–C bond cleavage of methylenecyclopropane. With the use of methylenecyclopropane possessing an acyclic alkyl substituent, this reaction was also accompanied by the β-hydrogen elimination.

  在三乙基硼烷存在下，烯酮或烯醛与亚甲基环丙烷的镍催化烷基化偶联是通过亚甲基环丙烷的立体定向近端C-C键裂解实现的。通过使用具有无环烷基取代基的亚甲基环丙烷，该反应还伴随有β-氢的消除。
• 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.