(R)-2-(1-cyclohexyl-1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)prop-2-en-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane | 827608-88-8

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 硼酸衍生物
• 英文名称: (R)-2-(1-cyclohexyl-1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)prop-2-en-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
• 英文别名: 2-[(1R)-1-cyclohexyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)prop-2-enyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
• CAS: 827608-88-8
• 化学式: C₂₁H₃₈B₂O₄
• 分子量: 376.152
• InChiKey: PVWLWFSLZJZCKJ-KRWDZBQOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.22
• 重原子数：
  27
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.9
• 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：

  (R)-2-(1-cyclohexyl-1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)prop-2-en-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 在 sodium hydroxide 、 水 、 双氧水 、 caesium carbonate 作用下， 以 四氢呋喃 、 水 、 甲苯 为溶剂， 反应 21.0h， 生成 (1R,2R)-1-cyclohexyl-3-phenylpropane-1,2-diol
  参考文献：
  名称：

  通过单锅艾伦二硼化/氢硼化/交叉偶联的模块式不对称合成1,2-二醇。

  摘要：

  手性烯丙基乙烯基硼酸酯是通过前手性烯丙基的催化对映选择性二硼化而生成的。然后可以使它们与硼氢化试剂原位反应以形成新型三硼中间体。然后受阻最少和反应性最强的CB键参与交叉偶联，其中偶联是通过与催化双硼化反应的催化剂相同的催化剂进行的。然后在反应后处理中将剩余的CB键氧化，从而允许以简明的单罐方式模块化合成手性二醇。

  DOI：

  10.1021/ol0616891
• 作为产物：
  描述：

  环己基丙二醇 、 联硼酸频那醇酯 在 tris-(dibenzylideneacetone)dipalladium(0) 作用下， 以 甲苯 为溶剂， 以92%的产率得到(R)-2-(1-cyclohexyl-1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)prop-2-en-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
  参考文献：
  名称：

  Development, Mechanism, and Scope of the Palladium-Catalyzed Enantioselective Allene Diboration

  摘要：

  In the presence of a chiral phosphoramidite ligand, the palladium-catalyzed diboration of allenes can be executed with high enantioselectivity. This reaction provides high levels of selectivity with a range of aromatic and aliphatic allene substrates. Isotopic-labeling experiments, stereodifferentiating reactions, kinetic analysis, and computational experiments suggest that the catalytic cycle proceeds by a mechanism involving rate-determining oxidative addition of the diboron to Pd followed by transfer of both boron groups to the unsaturated substrate. This transfer reaction most likely occurs by coordination and insertion of the more accessible terminal alkene of the allene substrate, by a mechanism that directly provides the eta(3) pi-allyl complex in a stereospecific, concerted fashion.

  DOI：

  10.1021/ja070572k

文献信息

• Concatenated Catalytic Asymmetric Allene Diboration/Allylation/Functionalization
  作者：Angela R. Woodward、Heather E. Burks、Louis M. Chan、James P. Morken

  DOI：10.1021/ol052312i

  日期：2005.11.1

  [reaction: see text] Palladium-catalyzed enantioselective diboration of prochiral allenes generates a reactive chiral allylboron intermediate which is a versatile reagent for the allylation of carbonyls. Experiments that improve the enantioselectivity of this process, examine the substrate scope, and are directed toward functionalization of the allylation intermediate are described.

  [反应：见正文]钯催化的前手性烯的对映选择性二硼化反应可生成反应性手性烯丙基硼中间体，该中间体是用于羰基烯丙基化的通用试剂。描述了改善该方法的对映选择性，检查底物范围并针对烯丙基化中间体的功能化的实验。
• Palladium-Catalyzed Enantioselective Diboration of Prochiral Allenes
  作者：Nicholas F. Pelz、Angela R. Woodward、Heather E. Burks、Joshua D. Sieber、James P. Morken

  DOI：10.1021/ja044167u

  日期：2004.12.1

  Pd-catalyzed diboration of prochiral allenes occurs exclusively at the internal position and is remarkably accelerated in the presence of Lewis basic ligand structures. On the basis of preliminary observations, a chiral ligand was employed, and the enantiomeric excess of a variety of diboration products was found to be in the range of 86-92% ee. The chiral diboron reaction products should be useful in organic synthesis, and preliminary experiments suggest that they may participate in allylation reactions with a high level of chirality transfer.
• Sequential Pd-Catalyzed Asymmetric Allene Diboration/α-Aminoallylation
  作者：Joshua D. Sieber、James P. Morken

  DOI：10.1021/ja057020r

  日期：2006.1.1

  Pd-catalyzed enantioselective diboration of prochiral allenes provides adducts which participate in highly selective allylation reactions with primary imines. The allylation product is a vinyl boronate which may be oxidized to give nonracemic Mannich products (87-97% ee). Alternatively, enantiomerically enriched homoallylic amine derivatives may be obtained by protonation and Suzuki cross-coupling of the vinyl boronate.
• Development, Mechanism, and Scope of the Palladium-Catalyzed Enantioselective Allene Diboration
  作者：Heather E. Burks、Shubin Liu、James P. Morken

  DOI：10.1021/ja070572k

  日期：2007.7.1

  In the presence of a chiral phosphoramidite ligand, the palladium-catalyzed diboration of allenes can be executed with high enantioselectivity. This reaction provides high levels of selectivity with a range of aromatic and aliphatic allene substrates. Isotopic-labeling experiments, stereodifferentiating reactions, kinetic analysis, and computational experiments suggest that the catalytic cycle proceeds by a mechanism involving rate-determining oxidative addition of the diboron to Pd followed by transfer of both boron groups to the unsaturated substrate. This transfer reaction most likely occurs by coordination and insertion of the more accessible terminal alkene of the allene substrate, by a mechanism that directly provides the eta(3) pi-allyl complex in a stereospecific, concerted fashion.
• Modular Asymmetric Synthesis of 1,2-Diols by Single-Pot Allene Diboration/Hydroboration/Cross-Coupling
  作者：Nicholas F. Pelz、James P. Morken

  DOI：10.1021/ol0616891

  日期：2006.9.1

  Chiral allyl vinyl boronates are generated by catalytic enantioselective diboration of prochiral allenes. They may then be reacted, in situ, with a hydroborating reagent to form a novel triboron intermediate. The least hindered and most reactive C-B bond then participates in cross-coupling wherein the coupling is brought about by the same catalyst as that which catalyzed the diboration reaction. The

  手性烯丙基乙烯基硼酸酯是通过前手性烯丙基的催化对映选择性二硼化而生成的。然后可以使它们与硼氢化试剂原位反应以形成新型三硼中间体。然后受阻最少和反应性最强的CB键参与交叉偶联，其中偶联是通过与催化双硼化反应的催化剂相同的催化剂进行的。然后在反应后处理中将剩余的CB键氧化，从而允许以简明的单罐方式模块化合成手性二醇。