2-[(Z)-2-cyclopropylethenyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane | 1394797-17-1

• 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: 2-[(Z)-2-cyclopropylethenyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
• CAS: 1394797-17-1
• 化学式: C₁₁H₁₉BO₂
• 分子量: 194.082
• InChiKey: FCWYPDPDAZGFRJ-FPLPWBNLSA-N

物化性质

• 沸点：
  201.6±23.0 °C(Predicted)
• 密度：
  0.95±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.58
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  环丙乙炔 、 频那醇硼烷 在 bis(norbornadiene)rhodium(l)tetrafluoroborate 、 2,7-di-tert-butyl-4,5-bis(diisopropylphosphino)-9,9-dimethylthioxanthene 作用下， 以 甲苯 为溶剂， 反应 4.0h， 以70%的产率得到2-[(Z)-2-cyclopropylethenyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
  参考文献：
  名称：

  (Z)-PSP-Pincer 铑配合物催化的末端炔烃的选择性硼氢化反应

  摘要：

  使用基于噻吨的 PSP-钳形铑催化剂实现了末端炔烃的高 ( Z ) 选择性硼氢化反应。与羰基化合物（如酮和醛）相比，这种硼氢化反应对炔烃表现出良好的化学选择性。机理研究表明铑-亚乙烯基中间体的参与，高（Z）选择性可归因于 PSP-铑催化剂的刚性和富电子性质。

  DOI：

  10.1021/acs.orglett.1c03606

文献信息

• Dearomatization and Functionalization of Terpyridine Ligands Leading to Unprecedented Zwitterionic Meisenheimer Aluminum Complexes and Their Use in Catalytic Hydroboration
  作者：Guoqi Zhang、Jing Wu、Haisu Zeng、Michelle C. Neary、Matthew Devany、Shengping Zheng、Pavel A. Dub

  DOI：10.1021/acscatal.8b04096

  日期：2019.2.1

  terpyridine (tpy) ligands via 2′/6′-, 3′/5′-, or 4′-selective alkylation of the central pyridine ring. The reaction is mediated by the most abundant metal in the Earth’s crust, aluminum (Al), and depending on the conditions employed, exhibits ionic or radical character as suggested by experimental and computational analysis. In the latter case, intermediate formation of an AlIII complex supported by π-radical

  本文报道了通过中央吡啶环的2'/ 6'-，3'/ 5'-或4'-选择性烷基化使遍在的吡啶（tpy）配体脱芳香化的第一个例子。该反应是由地壳中最丰富的金属铝（Al）介导的，并且根据所采用的条件，它表现出离子或自由基的特性，这是实验和计算分析所表明的。在后一种情况下，由π自由基单阴离子配体（tpy •）1–支撑的Al III络合物的中间形成是显而易见的。3'/ 5'-烷基化导致空前的两性离子迈森海默Al III配合物，被确定为选择性氢硼化C═O和C functionalC官能团的有效前催化剂。高达〜1000的周转数（TONs）使相应的络合物进入迄今为止报道的标题反应最有效的Al催化剂类别。获得的数据表明，一氢化铝或更可能是二氢化铝可能是相关的催化物质。或者，也可以想象一种机械化的情况，其中脱芳族化的“化学上无害的”配体充当氢化物供体，并且将来有必要对此进行详细研究。
• Cobalt Catalyzed <i>Z</i>-Selective Hydroboration of Terminal Alkynes and Elucidation of the Origin of Selectivity
  作者：Jennifer V. Obligacion、Jamie M. Neely、Aliza N. Yazdani、Iraklis Pappas、Paul J. Chirik

  DOI：10.1021/jacs.5b00936

  日期：2015.5.13

  A bis(imino)pyridine cotalt-catalyzed hydroboration of terminal,,alkynes with HBPin (Pin = pinacolate) with high yield and (Z)selectivity for synthetically valuable vinylboronate esters is described. Deuterium labeling studies Stoichiometric experiments, and isolation of catalytically relevant intermediats support a mechanism involving;selective insertion of,an alkynyl-boronate ester into a Co-H bond, a pathway distinct from known precious metal catalysts, where metal Vinylidene intermediates have been proposed to account for the observed (Z) selectivity. The identity Of the imine substituents dictates the relative rates of activation of the cobalt precatalyst with HBPin or the terminal alkyne and, as a consequence, is responsible for the stereochemical outcome of the catalytic reaction.
• Ruthenium Catalyzed Hydroboration of Terminal Alkynes to <i>Z</i>-Vinylboronates
  作者：Chidambaram Gunanathan、Markus Hölscher、Fangfang Pan、Walter Leitner

  DOI：10.1021/ja307233p

  日期：2012.9.5

  The nonclassical ruthenium hydride pincer complex [Ru(PNP)(H)(2)(H-2)] 1 (PNP = 1,3-bis(di-tert-butyl-phosphinomethyl)pyridine) catalyzes the anti-Markovnikov addition of pinacolborane to terminal alkynes yielding Z-vinylboronates at mild conditions. The complex [Ru(PNP)(H)(2)(HBpin)] 2 (HBpin = pinacolborane), which was identified at the end of the reaction and prepared independently, is proposed as the direct precursor to the catalytic cycle involving rearrangement of coordinated alkyne to Z-vinylidene as a key step for the apparent trans-hydroboration.