(dimethylphenylsilyl)((+)-pinanediolato)borane | 612836-12-1

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (dimethylphenylsilyl)((+)-pinanediolato)borane
• 英文别名: dimethyl-phenyl-[(1S,2S,6R,8S)-2,9,9-trimethyl-3,5-dioxa-4-boratricyclo[6.1.1.02,6]decan-4-yl]silane
• CAS: 612836-12-1
• 化学式: C₁₈H₂₇BO₂Si
• 分子量: 314.308
• InChiKey: HCFBXPRBNUEAFL-SCNOPHJPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.41
• 重原子数：
  22
• 可旋转键数：
  2
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.67
• 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：

  溴乙烯 、 (dimethylphenylsilyl)((+)-pinanediolato)borane 在 2,2,6,6-tetramethylpiperidinyl-lithium 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 以72%的产率得到1-dimethylphenylsilyl-1-[(3aS,4S,6S,7aR)-hexahydro-3a,5,5-trimethyl-4,6-methano-1,3,2-benzodioxaborol-2-yl]ethene
  参考文献：
  名称：

  Geminal dimetalation of alkylidene-type carbenoids with silylboranes and diborons

  摘要：

  A novel and efficient method for gem-dimetalation of carbenoids has been demonstrated. Treatment of alkylidene-type lithium carbenoids with such an interelement compound as silylborane or diboron to generate the corresponding borate complex, followed by warming to room temperature, induced migration of the silyl or boryl group from a negatively charged boron atom to the carbenoid carbon to afford 1-boryl-1-silyl-1-alkenes or 1,1-diboryl-1-alkenes in good yields. Carbon-carbon bond forming transformations of the gem-dimetalated compounds mediated by boron or silicon is also described. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(02)00648-8
• 作为产物：
  描述：

  dimethyl(phenyl)silyllithium 、 boron,4,6,6-trimethylbicyclo[3.1.1]heptane-4,5-diol 以 四氢呋喃 、 正己烷 为溶剂， 以64%的产率得到(dimethylphenylsilyl)((+)-pinanediolato)borane
  参考文献：
  名称：

  Geminal dimetalation of alkylidene-type carbenoids with silylboranes and diborons

  摘要：

  A novel and efficient method for gem-dimetalation of carbenoids has been demonstrated. Treatment of alkylidene-type lithium carbenoids with such an interelement compound as silylborane or diboron to generate the corresponding borate complex, followed by warming to room temperature, induced migration of the silyl or boryl group from a negatively charged boron atom to the carbenoid carbon to afford 1-boryl-1-silyl-1-alkenes or 1,1-diboryl-1-alkenes in good yields. Carbon-carbon bond forming transformations of the gem-dimetalated compounds mediated by boron or silicon is also described. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(02)00648-8

文献信息

• Enantioselective silicon–boron additions to cyclic 1,3-dienes catalyzed by the platinum group metal complexes
  作者：Martin Gerdin、Maël Penhoat、Raivis Zalubovskis、Claire Pétermann、Christina Moberg

  DOI：10.1016/j.jorganchem.2008.08.029

  日期：2008.11

  Silaborations of 1,3-cyclohexadiene and 1,3-cycloheptadiene were achieved using catalysts prepared from different combinations of phosphorus ligands and group 10 metal compounds. For the six-membered compound, 1,4-adducts with up to 82% ee were obtained employing Pt(0) and phosphoramidite ligands. For the seven-membered diene optimal conditions were found using catalysts based on Ni(0), but the highest

  使用由磷配体和第10族金属化合物的不同组合制备的催化剂实现了1,3-环己二烯和1,3-环庚二烯的硅烷化。对于六元化合物，使用Pt（0）和亚磷酰胺配体可获得ee高达82％的1,4-加合物。对于七元二烯，使用基于Ni（0）的催化剂发现了最佳条件，但观察到的最高选择性仅为22％ee。使用手性甲硅烷基硼烷与手性亚磷酰胺配体结合添加到1，3-环己二烯中，没有获得手性诱导的改善。由环己二烯获得的加合物在微波辐射下用于醛的烯丙基硼化中，以产生具有中等至良好非对映选择性的均烯丙基醇。
• Enantioface-Selective Palladium-Catalyzed Silaboration of Allenes via Double Asymmetric Induction
  作者：Michinori Suginome、Toshimichi Ohmura、Yoshihiro Miyake、Shin'ichirou Mitani、Yoshihiko Ito、Masahiro Murakami

  DOI：10.1021/ja0368958

  日期：2003.9.1

  Enantioenriched beta-borylallylsilanes were synthesized by palladium-catalyzed enantioface-selective addition of the silicon-boron bond to terminal allenes using a palladium catalyst possessing a chiral monodentate phosphine ligand. Use of a silylborane bearing a chiral auxiliary on the boron atom was beneficial to gain enantioface selectivities as high as 96% de.
• Asymmetric Silaboration of Terminal Allenes Bearing α-Stereogenic Centers:  Stereoselection Based on “Reagent Control”
  作者：Toshimichi Ohmura、Michinori Suginome

  DOI：10.1021/ol060666j

  日期：2006.6.1

  A highly enantioface-selective silaboration of allenes having stereogenic centers at the alpha-positions of the double bonds has been achieved using a combination of a chiral silylborane(-)-2 and a chiral Pd/(R)-3 catalyst. The chiral reagent system efficiently controlled the stereochemistry of the new stereogenic centers even in the reactions of mismatched combinations.
• Geminal dimetalation of alkylidene-type carbenoids with silylboranes and diborons
  作者：Takuya Kurahashi、Takeshi Hata、Hirokazu Masai、Hirotaka Kitagawa、Masaki Shimizu、Tamejiro Hiyama

  DOI：10.1016/s0040-4020(02)00648-8

  日期：2002.8

  A novel and efficient method for gem-dimetalation of carbenoids has been demonstrated. Treatment of alkylidene-type lithium carbenoids with such an interelement compound as silylborane or diboron to generate the corresponding borate complex, followed by warming to room temperature, induced migration of the silyl or boryl group from a negatively charged boron atom to the carbenoid carbon to afford 1-boryl-1-silyl-1-alkenes or 1,1-diboryl-1-alkenes in good yields. Carbon-carbon bond forming transformations of the gem-dimetalated compounds mediated by boron or silicon is also described. (C) 2002 Elsevier Science Ltd. All rights reserved.