(E)-4,4,5,5-tetramethyl-2-(oct-2-en-1-yl)-1,3,2-dioxaborolane | 1172607-87-2

• 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: (E)-4,4,5,5-tetramethyl-2-(oct-2-en-1-yl)-1,3,2-dioxaborolane
• 英文别名: 4,4,5,5-tetramethyl-2-[(E)-oct-2-enyl]-1,3,2-dioxaborolane
• CAS: 1172607-87-2
• 化学式: C₁₄H₂₇BO₂
• 分子量: 238.178
• InChiKey: NLQSKIHSKVCAOI-ZHACJKMWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.22
• 重原子数：
  17
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.86
• 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：

  (E)-4,4,5,5-tetramethyl-2-(oct-2-en-1-yl)-1,3,2-dioxaborolane 在 二氟化氢钾 作用下， 以 甲醇 、 水 为溶剂， 以158 mg的产率得到potassium trifluoro(2-octenyl)borate
  参考文献：
  名称：

  Performance of SCS Palladium Pincer Complexes in Borylation of Allylic Alcohols. Control of the Regioselectivity in the One-Pot Borylation−Allylation Process

  摘要：

  One-pot borylation-allylation reactions of aldehydes and allylic alcohols were performed under various reaction conditions. The borylation of allylic alcohols was performed using a very efficient SCS palladium pincer-complex catalyst. The regioselectivity of the allylation depends on the applied solvent. The reaction in CHCl3 gave the linear allylic product; however, when MeOH was added to the reaction mixture, the branched allylic product was formed.

  DOI：

  10.1021/jo9008673
• 作为产物：
  描述：

  4-辛炔 以 氘代苯 、 正戊烷 为溶剂， 反应 120.25h， 生成 (E)-4,4,5,5-tetramethyl-2-(oct-2-en-1-yl)-1,3,2-dioxaborolane
  参考文献：
  名称：

  铑介导的双（烷基）炔烃的脱氢硼氢化-加氢硼化：中间体和机理

  摘要：

  复杂的Rh（BPIN）{κ 3 -P，O，P- [xant（P我镨2）2 ]}（BPIN = pinacolboryl; xant（P我镨2）2 = 9,9-二甲基-4,5-双（二异丙基膦基）x吨）催化将B 2销2加到3-己炔和4-辛炔中，得到共轭硼烷基二烯和硼烷基烯烃的等分子混合物，这是由于乙硼烷的B–B键添加到不同分子上的结果炔烃和氢化物从一个转移到另一个。脱氢硼酸酯化反应和氢硼酸化反应均形成催化循环，该催化循环是根据化学计量研究推导的。复杂的Rh（BPIN）{κ 3 -P，O，P- [xant（P我镨2） 2 ]}由炔入的Rh-B键的插入反应的手段促进炔烃的脱氢硼基化， ž - ë所得的Rh-烯基物质的β-borylalkenyl配体的异构化，和C γ连接至烯基Cα原子的烷基取代基的-H键活化。作为boryldienes的形成的结果，一氢化RhH的{κ 3 -P，O，P- [xant（P我镨2）

  DOI：

  10.1021/acs.organomet.9b00104

文献信息

• Synthesis of Benzyl-, Allyl-, and Allenyl-boronates via Copper-Catalyzed Borylation of Alcohols
  作者：Lujia Mao、Kálmán J. Szabó、Todd B. Marder

  DOI：10.1021/acs.orglett.7b00256

  日期：2017.3.3

  Alcohols are among the most abundant and readily available organic feedstocks in industrial processes. The direct catalytic functionalization of sp3 C–O bonds of alcohols remains the main challenge in this field. Here, we report a copper-catalyzed synthesis of benzyl-, allyl-, and allenyl-boronates from benzylic, allylic, and propargylic alcohols, respectively. This protocol exhibits a broad reaction

  酒精是工业过程中最丰富，最容易获得的有机原料之一。醇的sp 3 C–O键的直接催化官能化仍然是该领域的主要挑战。在这里，我们报道了分别由苄基，烯丙基和炔丙基醇的铜催化的苄基，烯丙基和烯丙基硼酸酯的合成。该方案在温和的条件下（包括用于制备仲烯丙基硼酸酯）表现出宽泛的反应范围（40个实例）和高效（高达95％的产率）。初步的机理研究表明，该反应涉及亲核取代。
• Stereoselective Dehydroxyboration of Allylic Alcohols to Access (<i>E</i>)-Allylboronates by a Combination of C–OH Cleavage and Boron Transfer under Iron Catalysis
  作者：Wei Su、Ting-Ting Wang、Xia Tian、Jian-Rong Han、Xiao-Li Zhen、Shi-Ming Fan、Ya-Xin You、Yu-Kun Zhang、Rui-Xiao Qiao、Qiushi Cheng、Shouxin Liu

  DOI：10.1021/acs.orglett.1c03359

  日期：2021.12.3

  Iron-catalyzed direct SN2′ dehydroxyboration of allylic alcohols has been developed to access (E)-stereoselective allylboronates. Allylic alcohols with diverse structures and functional groups, especially derived from natural products, underwent smooth transformation. The six-membered ring transition state formed by allylic alcohols and iron–boron intermediate was indicated to be the key component

  铁催化的烯丙醇直接 S N 2' 脱羟基硼酸已被开发用于获得 ( E )-立体选择性烯丙基硼酸酯。具有多种结构和官能团的烯丙醇，特别是来自天然产物的烯丙醇，经历了平稳的转变。由烯丙醇和铁-硼中间体形成的六元环过渡态被证明是参与硼基团转移、C-OH键活化和立体选择性控制的关键成分。
• Palladium-Catalyzed Allylic C−OH Functionalization for Efficient Synthesis of Functionalized Allylsilanes
  作者：Nicklas Selander、Jennifer R. Paasch、Kálmán J. Szabó

  DOI：10.1021/ja1096732

  日期：2011.1.26

  A new method is described for palladium-catalyzed allylic silylation using allylic alcohols and disilanes as precursors. The reactions proceed smoothly under mild and neutral conditions, and this method is suitable for synthesis of regio- and stereodefined allylsilanes. The presented silylation reaction can be easily extended to include synthesis of allylboronates by change of the dimetallic reagent

  描述了一种使用烯丙醇和乙硅烷作为前体的钯催化烯丙基硅烷化的新方法。该反应在温和和中性条件下顺利进行，该方法适用于合成区域和立体定义的烯丙基硅烷。所提出的甲硅烷基化反应可以很容易地扩展到包括通过改变双金属试剂来合成烯丙基硼酸酯。所提出的合成程序为功能化烯丙基金属试剂的选择性合成提供了一个广泛的平台，这些试剂是高级有机化学和天然产物合成中的有用前体。
• Palladium-Catalyzed Oxidative Borylation of Allylic C–H Bonds in Alkenes
  作者：Lujia Mao、Rüdiger Bertermann、Simon G. Rachor、Kálmán J. Szabó、Todd B. Marder

  DOI：10.1021/acs.orglett.7b03296

  日期：2017.12.15

  palladium pincer complex-catalyzed allylic C–H borylation of alkenes. The transformation exhibits high regio- and stereoselectivity with a variety of linear alkenes. A synthetically useful feature of this allylic C–H borylation method is that all allyl-Bpin products can be isolated in usually high yields. Preliminary mechanistic studies indicate that this C–H borylation reaction proceeds via Pd(IV) pincer

  该交流描述了一种有效的钯夹钳络合物催化烯烃的烯丙基CH硼化。该转化对多种直链烯烃表现出高的区域选择性和立体选择性。这种烯丙基CH硼化方法的合成有用特性是，通常可以高收率分离出所有烯丙基-Bpin产物。初步的机理研究表明，这种C–H硼酸酯化反应是通过Pd（IV）夹杂物复杂的中间体进行的。
• Electrochemical preparation of pinacol allylboronic esters
  作者：Julien Godeau、Christine Pintaric、Sandra Olivero、Elisabet Duñach

  DOI：10.1016/j.electacta.2009.01.015

  日期：2009.9

  electroreduction of allylic halide derivatives in the presence of pinacolborane afforded allylboronic pinacol esters with moderate to good yields (up to 86%) and high regioselectivities. The electrosynthesis was carried out in a single-compartment cell with an Al anode, in THF at room temperature and it constitutes an alternative route for the preparation of allylboronic esters under mild conditions.

  在频哪醇硼烷的存在下对烯丙基卤化物衍生物进行电还原，得到了烯丙基硼酸频哪醇酯，具有中等至良好的收率（高达86％）和较高的区域选择性。电合成是在室温下在带有THF的单室电池中，在Al阳极中进行的，它构成了在温和条件下制备烯丙基硼酸酯的另一种方法。