4,4,5,5-tetramethyl-2-(2-methyl-pentyl)-[1,3,2]dioxaborolane | 1203488-28-1

• 英文名称: 4,4,5,5-tetramethyl-2-(2-methyl-pentyl)-[1,3,2]dioxaborolane
• 英文别名: 2-(2-methylpentyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane；CH3CH2CH2CH(CH3)CH2B(pinacolate)；CH3CH2CH2CH(CH3)CH2BPin
• CAS: 1203488-28-1
• 化学式: C₁₂H₂₅BO₂
• 分子量: 212.14
• InChiKey: FUYOJSIAYYAOIO-SNVBAGLBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.51
• 重原子数：
  15.0
• 可旋转键数：
  4.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  18.46
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为产物：
  描述：

  异己烯 、 频那醇硼烷 在 C₂₇H₄₈CoN₃PSi₂ 作用下， 以 neat (no solvent) 为溶剂， 反应 1.0h， 以90%的产率得到4,4,5,5-tetramethyl-2-(2-methyl-pentyl)-[1,3,2]dioxaborolane
  参考文献：
  名称：

  （N-膦酰胺基）钴催化的硼氢化反应：烯烃异构化Affords末端选择性

  摘要：

  在此，我们建立了三配位的（N-膦酰氨基din）钴（酰胺基）预催化剂的用途，该催化剂能够在室温下实现具有挑战性的烯烃异构化/氢硼化过程，从而导致硼基的选择性末端加成。

  DOI：

  10.1002/chem.201403945

文献信息

• Dramatic Effect of Lewis Acids on the Rhodium-Catalyzed Hydroboration of Olefins
  作者：Christopher J. Lata、Cathleen M. Crudden

  DOI：10.1021/ja904142m

  日期：2010.1.13

  The addition of Lewis acids such as trispentafluoroboron as cocatalysts has been found to have a dramatic effect on the Rh-catalyzed hydroboration of olefins with pinacol borane. For example, aliphatic olefins do not react at all in noncoordinating solvents, but with the addition of 2% of B(C(6)F(5))(3), the reaction is complete in minutes. Similarly, the reaction of aromatic olefins with HBPin occurs

  已发现添加路易斯酸如三五氟硼作为助催化剂对用频哪醇硼烷对烯烃进行 Rh 催化的硼氢化反应具有显着影响。例如，脂肪族烯烃在非配位溶剂中根本不反应，但加入 2% 的 B(C(6)F(5))(3) 后，反应可在几分钟内完成。同样，芳族烯烃与 HBPin 的反应在 B(C(6)F(5))(3) 不存在的情况下缓慢且非选择性地发生，但在 B(C(6)F(5))(3) 存在时会加速并更有选择性地发生。初步机理研究表明，B(C(6)F(5))(3) 需要在整个反应过程中存在，而不仅仅是在起始阶段，并且表明该物质与 THF 一起存在于异裂反应中HBPin 的 BH 键断裂。
• Iron-Catalyzed, Atom-Economical, Chemo- and Regioselective Alkene Hydroboration with Pinacolborane
  作者：Lei Zhang、Dongjie Peng、Xuebing Leng、Zheng Huang

  DOI：10.1002/anie.201210347

  日期：2013.3.25

  iron: A new PNN iron complex has been developed for use in an iron‐catalyzed alkene hydroboration reaction under mild conditions. The environmentally friendly and earth‐abundant iron catalyst system is superior to precious‐metal systems in terms of efficiency and selectivity for α‐olefin hydroborations with pinacolborane.

  贵铁：已开发出一种新的PNN铁络合物，可在温和条件下用于铁催化的烯烃加氢硼化反应。在对频哪醇硼烷进行α-烯烃加氢硼化反应的效率和选择性方面，环保且富含地球的铁催化剂体系优于贵金属体系。
• Low Oxidation State Cobalt Center Stabilized by a Covalent Organic Framework to Promote Hydroboration of Olefins
  作者：Luis Gutiérrez、Vlad Martin-Diaconescu、Carla Casadevall、Freddy Oropeza、Victor A. de la Peña O’Shea、JingJing Meng、Manuel A. Ortuño、Julio Lloret-Fillol

  DOI：10.1021/acscatal.2c05442

  日期：2023.3.3

  decomposition while creating catalysts with improved activity and robustness. The covalent organic framework (COF) based on single cobalt sites coordinated to 2,2′-bipyridine (COFbpyCo) exploits the isolated nature of the cobalt sites to stabilize low-valent single sites and catalyze the hydroboration of olefins. Terminal alkyl boronate esters were obtained using 1 mol % COFbpyCo loading starting from terminal

  网状材料内不稳定催化物质的位点隔离是一种有吸引力的策略，可减轻催化剂分解，同时产生具有更高活性和稳健性的催化剂。基于与 2,2'-联吡啶 ( COF bpy Co ) 配位的单个钴位点的共价有机框架 (COF) 利用钴位点的孤立性质来稳定低价单位点并催化烯烃的硼氢化反应。通过串联异构化-硼氢化过程，从末端烯烃和内部烯烃开始，使用 1 mol% COF bpy Co负载获得末端烷基硼酸酯。COF bpy Co的催化活性被回收六次后得到维护。实验和计算研究表明 (bpy •– )Co I (THF) 2 } 部分是 COF 中的活性催化物质。该机制遵循氧化硼基迁移，然后异构化和还原消除以形成硼酸酯。
• Cobalt- and Iron-Catalyzed Isomerization–Hydroboration of Branched Alkenes: Terminal Hydroboration with Pinacolborane and 1,3,2-Diazaborolanes
  作者：Takahiko Ogawa、Adam J. Ruddy、Orson L. Sydora、Mark Stradiotto、Laura Turculet

  DOI：10.1021/acs.organomet.6b00823

  日期：2017.1.23

  The synthesis and characterization of a series of structurally varied N-phosphinoamidinate-ligated cobalt complexes is described, along with the successful application of these and a related iron complex as precatalysts in the isomerization hydroboration of terminal, geminal, and internal alkenes. These reactions proceed under mild conditions (23-65 degrees C), at relatively low base-metal loadings (1-5 mol %), typically without cosolvent, and with high terminal hydroboration selectivity across a broad spectrum of branched alkenes. With some of the alkene substrates examined, the Nphosphinoamidinate-ligated precatalysts employed herein are shown to provide alternative terminal selectivity versus other previously reported precatalyst classes for such transformations. Reports of terminal-selective metal-catalyzed alkene isomerization hydroboration disclosed thus far in the literature employ pinacolborane (HBPin); while effective in the system herein, we also report the first examples of such transformations employing either 1,3-dimethyl-1,3-diaza-2-boracydopentane or benzo-1,3,2-diazaborolane. The application of these 1,3,2-diazaborolanes in place of HBPin in some instances enables novel terminal selectivity in the isomerization hydroboration of branched alkenes.
• High-Activity Cobalt Catalysts for Alkene Hydroboration with Electronically Responsive Terpyridine and α-Diimine Ligands
  作者：W. Neil Palmer、Tianning Diao、Iraklis Pappas、Paul J. Chirik

  DOI：10.1021/cs501639r

  日期：2015.2.6

  Cobalt alkyl complexes bearing readily available and redox-active 2,2':6',2"-terpyridine and a-diimine ligands have been synthesized, and their electronic structures have been elucidated. In each case, the supporting chelate is reduced to the monoanionic, radical form that is engaged in antiferromagnetic coupling with the cobalt(II) center. Both classes of cobalt alkyls proved to be effective for the isomerization hydroboration of sterically hindered alkenes. An a-diimine-substituted cobalt allyl complex proved exceptionally active for the reduction of hindered tri-, tetra-, and limonene, formation of an eta(3)-allyl complex with a C-H agostic interaction was identified and accounts for the sluggish reactivity observed with diene substrates. For the terpyridine derivative, unique Markovnikov selectivity with styrene was also observed with HBPin.