isopinocampheyl boron dichloride | 121326-42-9

• 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: isopinocampheyl boron dichloride
• 英文别名: isopinocampheylboron dichloride；isopinocampheyldichloroborane；isopinocamphenylBCl2；IpcBCl2；dichloro-[(1R,2S,3R,5R)-2,6,6-trimethyl-3-bicyclo[3.1.1]heptanyl]borane
• CAS: 121326-42-9
• 化学式: C₁₀H₁₇BCl₂
• 分子量: 218.962
• InChiKey: XIHICGVHMJJZAA-BZNPZCIMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.02
• 重原子数：
  13
• 可旋转键数：
  0
• 环数：
  3.0
• 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：

  isopinocampheyl boron dichloride 在 lithium aluminium tetrahydride 、 三甲基硅烷 作用下， 以 乙醚 为溶剂， 反应 0.5h， 生成 (+)-α-蒎烯
  参考文献：
  名称：

  Chiral Synthesis via Organoboranes. 48. Efficient Synthesis of Trans-Fused Bicyclic and Cyclic Ketones and Secondary Alcohols in High Optical Purities via Asymmetric Cyclic Hydroboration with Isopinocampheylchloroborane Etherate

  摘要：

  Highly stereo- and enantioselective annelation has been achieved for the synthesis of trans-fused bicyclic and cyclic ketones via the asymmetric cyclic hydroboration of suitable cyclic dienes, such as 1-allyl-1-cycloalkenes or 1-vinyl-1-cycloalkenes and appropriate acyclic 1,4-dienes, respectively, with enantiomerically pure isopinocampheylchloroborane etherate (IpcBHCl . Et2O). The IpcBHCl . Et2O (an 86-90% equilibrium mixture) was readily synthesized by the reaction of an equivalent amount of hydrochloric acid in ethyl ether (Et2O) with optically pure isopinocampheylborane (IpcBH(2)). The hydroboration of the terminal double bond of a representative diene with IpcBHCl . Et2O readily provided the corresponding isopinocampheylalkylchloroborane (IpcRBCl). Subsequent, hydridation of the IpcRBCl with lithium aluminum hydride (LAH, 0.25 equiv) at -20 or -25 degrees C generated the intermediate isopinocampheylalkylborane (IpcRBH) almost instantly, which then underwent a rapid stereospecific and enantioselective intramolecular cyclic hydroboration to provide the intermediate cyclic trialkylborane. This trialkylborane, on treatment with an aldehyde, liberated the optically pure auxiliary as a-pinene (readily recovered for recycle) to provide the corresponding cyclic borinate ester. This ester reacted smoothly with alpha,alpha-dichloromethyl methyl ether (DCME) in the presence of a hindered base (the DCME reaction) to yield, after oxidation with buffered hydrogen peroxide, the trans-fused bicyclic or cyclic ketone in high enantiomeric excess (ee). In another improved approach, in situ generated IpcBHCl . Et2O, from the reduction of isopinocampheyldichloroborane (IpcBCl(2)) with trimethylsilane (Me3SiH), in the presence of representative dienes in Et2O provided considerably improved optical yields of the bicyclic and cyclic ketones. The trialkylboranes obtained from suitable acyclic dienes can be easily protonolyzed to provide the secondary alcohols in high ee.

  DOI：

  10.1021/jo981040c
• 作为产物：
  描述：

  Pinene 在 三甲基硅烷 、 三氯化硼 作用下， 以 正戊烷 为溶剂， 生成 isopinocampheyl boron dichloride
  参考文献：
  名称：

  通过有机ob酸酯的手性合成。47.使用（+/-）-异樟脑基二氯硼烷有效合成不对称酮和对映体纯的螺缩酮。

  摘要：

  现成的且稳定的（+/-）-异樟脑基二氯硼烷[（+/-）-IpcBCl（2）]使用原位还原-氢硼化方案方便地用于两个不同烯烃的逐步氢硼化，从而得到混合的三烷基硼烷IpcBR（1 R（2）。通过用醛RCHO处理从这些三烷基硼烷中方便地消除α-pine烯，提供了硼酸酯R（1）R（2）BOCH（2）R。通过建立的方法，该中间体很容易以高收率和高纯度转化为不对称酮R（1）COR（2）。该方法已成功地应用于光学纯的TBS醚保护的均烯丙基醇作为烯烃进行逐步硼氢化的对映体纯螺环酮的合成。

  DOI：

  10.1021/jo980989w
• 作为试剂：
  描述：

  1-己烯 、 1,1-二氯甲醚 、 4-乙烯基-1-环己烯 在 lithium aluminium tetrahydride 、 三甲基硅烷 、 双氧水 、 sodium acetate 、 lithium 3-ethylpentan-3-olate 、 异丁醛 、 isopinocampheyl boron dichloride 作用下， 生成 1-(3-cyclohexenyl)-3-nonanone
  参考文献：
  名称：

  使用（±）-异樟脑基二氯硼烷通过烯烃的逐步硼氢化有效合成不对称酮

  摘要：

  已经开发出一种方便的一锅合成不对称酮的方法，该方法利用原位还原-易于制备且稳定的（±）-异樟脑基二氯硼烷进行硼氢化反应。

  DOI：

  10.1016/0040-4039(96)00161-x

文献信息

• Efficient Synthesis of B-Iododialkyl- and B-Alkyldiiodoboranes as Their Acetonitrile Complexes: Application for the Enolboration–Aldolization of Ethyl Ketones
  作者：P. Veeraraghavan Ramachandran、Mu-Fa Zou、Herbert C. Brown

  DOI：10.1002/1522-2675(200210)85:10<3027::aid-hlca3027>3.0.co;2-h

  日期：2002.10

  MeCN complexes from the corresponding chloro- and bromoboranes by treatment with NaI or KI in MeCN. In the presence of EtN(i-Pr)2, the B-(cyclohexyldiiodo)borane-acetonitrile complex converts ethyl ketones exclusively to the (Z)-enolates, which, upon aldolization with a series of aldehydes, provide the corresponding syn-aldols exclusively in high yields.

  通过在 MeCN 中用 NaI 或 KI 处理，一系列 B-（碘二烷基）硼烷和 B-（烷基二碘）硼烷已容易地从相应的氯代和溴代硼烷合成为 MeCN 配合物。在 EtN(i-Pr)2 存在下，B-(环己基二碘代)硼烷-乙腈络合物将乙基酮仅转化为 (Z)-烯醇化物，后者在与一系列醛醛缩合后提供相应的顺醛醇只在高产。
• A Chiral Alkyltris(pyrazolyl)borate Ligand:  Synthesis of [(Ipc)B(pz)₃Mn(CO)₃] and [(Ipc)B(pz)₃Ru(<i>p</i>-cymene)]PF₆ (Ipc = Isopinocampheyl)
  作者：Philip J. Bailey、Pedro Pinho、Simon Parsons

  DOI：10.1021/ic035061n

  日期：2003.12.1

  (Ipc)BCl(2) (Ipc = isopinocampheyl) in the synthesis of a new tris(pyrazolyl)borate ligand having an Ipc substituent on boron is described. The sodium salt is a convenient precursor for the preparation of the complexes [(Ipc)tris(pyrazolyl)borato]tricarbonylmanganese and [[(Ipc)tris(pyrazolyl)borato](p-cymene)ruthenium](+), whose X-ray crystal structures are reported. While little distortion of the B(pz)(3)M

  描述了试剂（Ipc）BCl（2）（Ipc =异樟脑基）在合成在硼上具有Ipc取代基的新的三（吡唑基）硼酸酯配体中的应用。钠盐是制备[[Ipc]三（吡唑基）硼酸酯]三羰基锰和[[[Ipc]三（吡唑基）硼酸酯]（对异丙基）钌]（+）的配合物的方便前体。报告了射线晶体结构。虽然在这些络合物中观察到的B（pz）（3）M单元几乎没有畸变，但Ipc基团和吡唑基环的3位之间的空间相互作用被认为会导致BC键周围的角度畸变。
• Hydroboration. 96. Synthesis and Chemistry of Sterically Modified α-Pinene-Related 2-Organylapoisopinocampheylchloro- and -bromoboranes, Potentially Valuable for Asymmetric Hydroboration
  作者：Ulhas P. Dhokte、Herbert C. Brown

  DOI：10.1021/om980172t

  日期：1998.6.1

  Optically pure and sterically varied 2-organylapoisopinocampheylchloro- and -bromoboranes (RapBHX; X = Cl and Br; R = Et (EapBHX), Pr (PraBHX), i-Bu (i-BapBHX), Ph (PapBHX), and i-Pr (i-PraBHX)), potentially valuable for asymmetric hydroboration of prochiral alkenes, are conveniently prepared by a number of simple approaches from the corresponding 2-organylapoisopinocampheyldihaloboranes (RapBX(2)) and 2-organylapoisopinocampheylboranes (RapBH(2)). All of these reagents can be readily obtained from 2-organylapopinenes (2-R-apopinenes). Increasing the steric bulk at the 2-position of the apopinene moiety significantly influences the formation of the desired RapBHCl. Thus, when R = i-Pr, a significantly lower amount of the sterically bulkier alkylchloroborane reagent, i-PraBHCl (47-52%), is formed in equilibrium with i-PraBH(2) (22-23%) and i-PraBCl(2) (22-23%). Surprisingly, a higher equilibrium composition for PapBHCl (84-86%, a sterically demanding borane reagent, is observed in equilibrium with 7-8% each of PapBH(2) and PapBCl(2). This result closely resembles the values realized in the formation of IpcBHCl, the least sterically hindered reagent among the organylchloroboranes examined in this study. However, it is possible to shift this equilibrium conveniently to achieve an increased concentration of RapBHCl (>95%) in ethyl ether (Et2O) in the presence of known amounts (1-4 equiv) of strongly coordinating solvents (CS), such as dimethyl sulfide (SMe2) and tetrahydrofuran (THF), solvents which readily coordinate with the chloroborane intermediates. Interestingly, irrespective of the bulk at the 2-position of the apopinene structure, the mere replacement of chloride in the RapBHCl reagents by bromide provides essentially pure RapBHBr. CS (95%, R = Me, Et, Pr, i-Bu, Ph, and i-Pr; CS = Et2O, THF, and SMe2) reagents.
• Synthesis of <i>N</i>-Alkyl/Aryl-<i>α</i>/<i>β</i>-Aminoalkylphosphonic Acids from Organodichloroboranes and <i>α</i>/<i>β</i>-Azidoalkylphosphonates via Polyborophosphonates
  作者：Jacques Mortier、Ilya D. Gridnev、Anne-Dominique Fortineau

  DOI：10.1021/ol990773w

  日期：1999.10.1

  [GRAPHICS]N-Alkyl/aryl-alpha- and beta-aminoalkylphosphonic acids can be effectively prepared by reductive alkylation of azidoalkylphosphonates with organodichloroboranes. The reaction is accompanied by simultaneous dealkylation of the phosphonates occurring via polyborophosphonates.
• Chiral Synthesis via Organoboranes. 47. Efficient Synthesis of Unsymmetrical Ketones and Enantiomerically Pure Spiroketals Using (±)-Isopinocampheyldichloroborane
  作者：Herbert C. Brown、Shekhar V. Kulkarni、Uday S. Racherla、Ulhas P. Dhokte

  DOI：10.1021/jo980989w

  日期：1998.10.1

  intermediate was readily converted into the unsymmetrical ketones, R(1)COR(2), in high yields and purity, by an established method. This methodology was successfully applied to the synthesis of enantiomerically pure spiroketals using optically pure TBS ether protected homoallylic alcohols as the alkenes for stepwise hydroboration.

  现成的且稳定的（+/-）-异樟脑基二氯硼烷[（+/-）-IpcBCl（2）]使用原位还原-氢硼化方案方便地用于两个不同烯烃的逐步氢硼化，从而得到混合的三烷基硼烷IpcBR（1 R（2）。通过用醛RCHO处理从这些三烷基硼烷中方便地消除α-pine烯，提供了硼酸酯R（1）R（2）BOCH（2）R。通过建立的方法，该中间体很容易以高收率和高纯度转化为不对称酮R（1）COR（2）。该方法已成功地应用于光学纯的TBS醚保护的均烯丙基醇作为烯烃进行逐步硼氢化的对映体纯螺环酮的合成。