(±)-2-(hex-1-en-3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane | 1174919-02-8

• 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: (±)-2-(hex-1-en-3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
• 英文别名: 2-(hex-1-en-3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane；2-(hex-1-ene-3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
• CAS: 1174919-02-8
• 化学式: C₁₂H₂₃BO₂
• 分子量: 210.124
• InChiKey: HOCVDXQMUXMTEZ-JTQLQIEISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.43
• 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：
  0.83
• 拓扑面积：
  18.46
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  (±)-2-(hex-1-en-3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 在 [RuHCl(CO)(PPh₃)₃] 作用下， 以 四氢呋喃 为溶剂， 反应 16.0h， 以95%的产率得到
  参考文献：
  名称：

  Ru催化ω-烯基硼酸酯的异构化反应对乙烯基硼酸酯的立体选择性合成以及随后的原位官能化

  摘要：

  通过钌催化的异构化反应，可以从ω-烯基硼酸酯中立体选择性地制备合成用途的乙烯基硼酸酯。可以方便地生产各种二取代和三取代的乙烯基硼酸酯，它们可以用作随后通过连续Ru / Pd或Ru / Cu双催化系统进行原位远程官能化的新起点。

  DOI：

  10.1039/d0sc02542a
• 作为产物：
  描述：

  反式-2-已烯-1-醇 在 甲醇 、 copper(l) iodide 、 1,10-菲罗啉 、 环辛烷 、 ((2S,3S)-6-mesityl-2,3-diphenyl-2,3,5,6-tetrahydroimidazo[1,2-c]quinazolin-5-yl)copper(I) chloride 、 caesium carbonate 、 sodium t-butanolate 作用下， 以 乙醚 、 甲苯 为溶剂， 反应 48.33h， 生成 (±)-2-(hex-1-en-3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
  参考文献：
  名称：

  Stereoconvergent Synthesis of Chiral Allylboronates from an E/Z Mixture of Allylic Aryl Ethers Using a 6-NHC−Cu(I) Catalyst

  摘要：

  We present a 6-NHC-Cu(I) complex that provides alpha-substituted allylboronates using allylic aryl ether substrates. The method was discovered by comparison of the chemoselectivities exhibited by complexes 1a, 1b, 2, and 3. We observed that 1a preferentially reacts with electron-rich alkenes over electron-deficient alkenes. Development of an asymmetric method revealed that 1b reacts with both the E and Z isomers to provide the same absolute configuration without showing E-Z isomerization. This stereoconvergent reaction occurs with high yields (av 86%), high S(N)2` selectivity (> 99:1), and high ee (av 94%) and exhibits wide functional-group tolerance using pure E or Z isomer or E/Z alkene mixtures. The stereoconvergent feature enables the use of many different olefination strategies for substrate production, including cross-metathesis. Chiral allylboronates could be purified by silica gel chromatography and stored in the freezer without decomposition.

  DOI：

  10.1021/ja1112518

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。
• Six-membered N-Heterocyclic Carbene-based catalysts for asymmetric reactions
  申请人：McQuade D. Tyler

  公开号：US20110054170A1

  公开（公告）日：2011-03-03

  The present invention provides a catalyst complex or ligand, and compositions thereof, for use in a variety of organic reactions having high reactivity and enantioselectivity. The catalyst is a N-heterocyclic carbene having three fused rings with first and second rings being six-membered rings and the third being a five-membered ring. The first ring is fused to the second and has four substituents. The second ring has two nitrogens flanking a carbene atom with one nitrogen bound to a substituent. The carbene atom may optionally be bonded to a metal. The third ring is fused to the second ring and contains two nitrogens. The third ring of the catalyst has a double bond and two substituents on adjacent non-fused carbons. A non-fused nitrogen of the third ring is partially bonded to another substituent. Methods for the synthesis and use of the catalyst embodiments of the present invention are also provided.

  本发明提供了一种催化剂复合物或配体，以及用于各种具有高反应性和对映选择性的有机反应的组合物。该催化剂是一种具有三个融合环的N-杂环卡宾，其中第一和第二环为六元环，第三环为五元环。第一环与第二环融合，并具有四个取代基。第二环具有两个氮原子夹着一个卡宾原子，其中一个氮原子与一个取代基结合。卡宾原子可以选择性地与金属结合。第三环与第二环融合，含有两个氮原子。催化剂的第三环具有一个双键，并且相邻的非融合碳上有两个取代基。第三环的非融合氮部分与另一个取代基部分结合。本发明还提供了有关合成和使用本发明催化剂实施例的方法。
• 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。
• Highly Stereoselective Synthesis of<i>Z</i>-Homoallylic Alcohols by Kinetic Resolution of Racemic Secondary Allyl Boronates
  作者：Celia A. Incerti-Pradillos、Mikhail A. Kabeshov、Andrei V. Malkov

  DOI：10.1002/anie.201300709

  日期：2013.5.10

  α to Z: Racemic α‐chiral allyl boronates, which are readily synthesized from the respective primary allyl halides, undergo a highly efficient kinetic resolution in a face‐ and Z‐selective allylation of aldehydes catalyzed by the chiral Brønsted acid (R)‐TRIP (see scheme; Epin=tetraethylethylene glycol).

  α到 Z：外消旋的α-手性烯丙基硼酸酯，很容易从相应的伯烯丙基卤化物合成，在手性布朗斯台德酸（R）-TRIP催化的醛的Z面和Z选择性烯丙基化反应中经历高效的动力学拆分（参见方案； Epin ＝四乙基乙二醇）。