2-[(Z)-5-(methyl)-1-hexenyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane | 1394797-13-7

• 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)-5-(methyl)-1-hexenyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
• 英文别名: (Z)-4,4,5,5-tetramethyl-2-(5-methylhex-1-en-1-yl)-1,3,2-dioxaborolane；4,4,5,5-tetramethyl-2-(5-methylhex-1-en-1-yl)-1,3,2-dioxaborolane；4,4,5,5-tetramethyl-2-[(Z)-5-methylhex-1-enyl]-1,3,2-dioxaborolane
• CAS: 1394797-13-7
• 化学式: C₁₃H₂₅BO₂
• 分子量: 224.151
• InChiKey: DUVNQVZLTLDVGL-NTMALXAHSA-N

物化性质

• 沸点：
  237.0±23.0 °C(predicted)
• 密度：
  0.88±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.61
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-[(Z)-5-(methyl)-1-hexenyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 在 四氮唑 、 四(三苯基膦)钯 、 thallium(I) carbonate 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 、 乙腈 为溶剂， 反应 17.5h， 生成 diallyl ((1E,4S,5S,6S,7Z,9Z)-6-((4-methoxybenzyl)oxy)-1-((2S,3S)-3-((4-methoxybenzyl)oxy)-6-oxo-3,6-dihydro-2H-pyran-2-yl)-5,13-dimethyltetradeca-1,7,9-trien-4-yl) phosphate
  参考文献：
  名称：

  Phosdiecin A 通过不对称醇介导的羰基还原偶联的全合成和结构验证

  摘要：

  phosdiecin A 的首次全合成和结构验证是通过不对称铱催化的醇介导的羰基还原偶联分 13 个步骤完成的。目前的路线是在超过 30 种全合成和正式合成中最短的。

  DOI：

  10.1021/jacs.9b07512
• 作为产物：
  描述：

  5-甲基-1-已炔 、 频那醇硼烷 在 C₂₂H₄₅NP₂Ru 作用下， 以 neat (no solvent) 为溶剂， 反应 24.08h， 以84%的产率得到2-[(Z)-5-(methyl)-1-hexenyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
  参考文献：
  名称：

  Ruthenium Catalyzed Hydroboration of Terminal Alkynes to Z-Vinylboronates

  摘要：

  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.

  DOI：

  10.1021/ja307233p

文献信息

• 10.1021/acscatal.4c03805
  作者：Zobernig, Daniel P.、Stöger, Berthold、Veiros, Luis F.、Kirchner, Karl

  DOI：10.1021/acscatal.4c03805

  日期：——

  Mn(I)-catalyzed hydroboration of terminal alkynes with pinacolborane (HBPin) is described. The hydroboration reaction is highly Z-selective in the case of aryl alkynes and E-selective in the case of aliphatic alkynes. The reaction requires no additives or solvents and proceeds with a catalyst loading of 1 mol % at 50–70 °C. The most active precatalyst is the bench-stable alkyl Mn(I) complex cis-[Mn(PCP

  描述了末端炔烃与频那醇硼烷 (HBPin) 的立体和区域选择性 Mn(I) 催化硼氢化反应。硼氢化反应在芳基炔的情况下具有高度Z-选择性，在脂族炔的情况下具有E-选择性。该反应不需要添加剂或溶剂，催化剂负载量为 1 mol%，反应温度为 50–70 °C。最活跃的预催化剂是工作台稳定的烷基Mn(I)络合物顺式-[Mn(PCP- i Pr)(CO) 2 (CH 2 CH 2 CH 3 )]。通过将CO配体迁移插入M n -烷基键中以产生酰基中间体来引发催化过程。该物质经历炔烃（芳香族炔烃）和 HBPin（脂肪族炔烃）的 C–H 和 B–H 键断裂，形成活性 Mn(I) 炔基和硼基催化剂 [Mn(PCP- i Pr)(CO )(C=CR)]和[Mn(PCP- i Pr)(CO)(BPin)]，分别。多种芳香族和脂肪族炔烃被有效且选择性地硼酸化。基于实验数据和 DFT 计算提供了机理见解。官能化烯烃可用于交叉偶联反应中的进一步应用。
• 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.
• 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.
• Total Synthesis and Structural Validation of Phosdiecin A via Asymmetric Alcohol-Mediated Carbonyl Reductive Coupling
  作者：Franco Della-Felice、Ariel M. Sarotti、Michael J. Krische、Ronaldo A. Pilli

  DOI：10.1021/jacs.9b07512

  日期：2019.9.4

  The first total synthesis and structural validation of phosdiecin A was accomplished in 13 steps through asymmetric iridium-catalyzed alcohol-mediated carbonyl reductive coupling. The present route is the shortest among >30 total and formal syntheses of fostriecin family members.

  phosdiecin A 的首次全合成和结构验证是通过不对称铱催化的醇介导的羰基还原偶联分 13 个步骤完成的。目前的路线是在超过 30 种全合成和正式合成中最短的。