(-)-di-2-isocaranylchloroborane | 154198-78-4

• 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: (-)-di-2-isocaranylchloroborane
• 英文别名: chloro-bis[(1S,2R,3S,6R)-3,7,7-trimethyl-2-bicyclo[4.1.0]heptanyl]borane
• CAS: 154198-78-4
• 化学式: C₂₀H₃₄BCl
• 分子量: 320.754
• InChiKey: ZPPFAIYJLFRWAW-OVSMWIARSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.36
• 重原子数：
  22
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  (-)-di-2-isocaranylchloroborane 、 alkaline earth salt of/the/ methylsulfuric acid 在 sodium hydroxide 、 双氧水 作用下， 以 乙醚 为溶剂， 生成
  参考文献：
  名称：

  Boroxy Fischer Carbene 配合物的分子内 C-H 插入反应。萜烯的区域选择性和非对映选择性修饰

  摘要：

  原位生成的二烷基硼氧基和二氨基硼氧基 Fischer 卡宾配合物通过分子内 CH 插入反应生成氧杂硼烷或氧杂硼烷衍生物。这些中间体的进一步氧化产生 1,3-二醇或 1,2-氨基醇衍生物。当从萜烯衍生的硼氧基 Fischer 卡宾配合物开始时，非对映选择性高达 99%，这代表了此类天然产物的区域和非对映选择性修饰。研究了Cβ取代基相对于硼原子对反应路径的影响，并在核磁共振鉴定中间体后提出了机理。此外，理论计算表明存在硼-金属相互作用，这可能是 C-H 插入反应的关键步骤。

  DOI：

  10.1021/ja991161+
• 作为产物：
  描述：

  (+)-2-carene 在 chloroborane methyl sulfide complex 作用下， 以 二氯甲烷 为溶剂， 反应 12.0h， 生成 (-)-di-2-isocaranylchloroborane
  参考文献：
  名称：

  Asymmetric ring opening of meso-epoxides with B-halobis(2-isocaranyl)boranes 2-dIcr2BX

  摘要：

  Hydroboration of commercially available (+)-2-carene (96% ee) with either BH2Cl center dot SMe2 or BC13/Me3SiH, provides chemically pure B-chlorobis(2-isocaranyl)borane (2-(d)Icr(2)BCl) whereas B-bromobis(2-isocaranyl)borane (2-(d)Icr(2)BBr) could only be prepared by Matteson's BBr3/Me3SiH procedure in high chemical yield and purity. The enantionteric excess achieved with 2-(d)Icr(2)BCl (78%), was significantly higher than those realized with the previously explored reagent, (IPC2BCl)-I-d (41%), especially for meso-cyclohexene oxide. The new reagent, 2-(d) Icr(2)BBr also showed considerable improvements in enantiomeric excesses, in the cases of meso-cyclopentene oxide (67%) and meso-cis-2,3-butene oxide (78%) than those achieved with the previously reported reagent, (IPC2BBr)-I-d (57% and 61%, respectively). (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2006.06.044

文献信息

• Fringuelli, Francesco; Martinetti, Evelina; Piermatti, Oriana, Gazzetta Chimica Italiana, 1993, vol. 123, # 11, p. 637 - 640
  作者：Fringuelli, Francesco、Martinetti, Evelina、Piermatti, Oriana、Pizzo, Ferdinando

  DOI：——

  日期：——
• Asymmetric ring opening of meso-epoxides with B-halobis(2-isocaranyl)boranes 2-dIcr2BX
  作者：Chandra D. Roy、Herbert C. Brown

  DOI：10.1016/j.tetasy.2006.06.044

  日期：2006.8

  Hydroboration of commercially available (+)-2-carene (96% ee) with either BH2Cl center dot SMe2 or BC13/Me3SiH, provides chemically pure B-chlorobis(2-isocaranyl)borane (2-(d)Icr(2)BCl) whereas B-bromobis(2-isocaranyl)borane (2-(d)Icr(2)BBr) could only be prepared by Matteson's BBr3/Me3SiH procedure in high chemical yield and purity. The enantionteric excess achieved with 2-(d)Icr(2)BCl (78%), was significantly higher than those realized with the previously explored reagent, (IPC2BCl)-I-d (41%), especially for meso-cyclohexene oxide. The new reagent, 2-(d) Icr(2)BBr also showed considerable improvements in enantiomeric excesses, in the cases of meso-cyclopentene oxide (67%) and meso-cis-2,3-butene oxide (78%) than those achieved with the previously reported reagent, (IPC2BBr)-I-d (57% and 61%, respectively). (c) 2006 Elsevier Ltd. All rights reserved.
• Intramolecular C−H Insertion Reactions of Boroxy Fischer Carbene Complexes. Regio- and Diastereoselective Modification of Terpenes
  作者：José Barluenga、Félix Rodríguez、Jérôme Vadecard、Maximilian Bendix、Francisco J. Fañanás、Fernando López-Ortiz、Miguel A. Rodríguez

  DOI：10.1021/ja991161+

  日期：1999.9.1

  In-situ-generated dialkylboroxy and diaminoboroxy Fischer carbene complexes lead to oxaborolane or oxazaborolidine derivatives via an intramolecular C−H insertion reaction. Further oxidation of these intermediates yields 1,3-diol or 1,2-amino alcohol derivatives. Diastereoselectivities as high as 99% are reached when starting from boroxy Fischer carbene complexes derived from terpenes, which represents a regio-

  原位生成的二烷基硼氧基和二氨基硼氧基 Fischer 卡宾配合物通过分子内 CH 插入反应生成氧杂硼烷或氧杂硼烷衍生物。这些中间体的进一步氧化产生 1,3-二醇或 1,2-氨基醇衍生物。当从萜烯衍生的硼氧基 Fischer 卡宾配合物开始时，非对映选择性高达 99%，这代表了此类天然产物的区域和非对映选择性修饰。研究了Cβ取代基相对于硼原子对反应路径的影响，并在核磁共振鉴定中间体后提出了机理。此外，理论计算表明存在硼-金属相互作用，这可能是 C-H 插入反应的关键步骤。