(Z)-4,4,5,5-tetramethyl-2-(pent-1-enyl)-1,3,2-dioxaborolane | 1352747-94-4

• 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: (Z)-4,4,5,5-tetramethyl-2-(pent-1-enyl)-1,3,2-dioxaborolane
• 英文别名: (Z)-1-pentenylboronic pinacolate；(Z)-2-(1-pentenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane；4,4,5,5-tetramethyl-2-[(Z)-pent-1-enyl]-1,3,2-dioxaborolane
• CAS: 1352747-94-4
• 化学式: C₁₁H₂₁BO₂
• 分子量: 196.098
• InChiKey: IMIHEZMTQOARIK-HJWRWDBZSA-N

物化性质

• 沸点：
  201.2±23.0 °C(Predicted)
• 密度：
  0.88±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.97
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• 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

• 作为反应物：
  描述：

  (Z)-4,4,5,5-tetramethyl-2-(pent-1-enyl)-1,3,2-dioxaborolane 、 2-碘-N,N-二乙基苯甲酰胺 在 四(三苯基膦)钯 、 sodium hydroxide 作用下， 以 1,4-二氧六环 、 水 为溶剂， 反应 3.0h， 以99%的产率得到(Z)-N,N-diethyl-2-(pent-1-enyl)benzamide
  参考文献：
  名称：

  Regiodivergent Iodocyclizations for the Highly Diastereoselective Synthesis of syn- and anti-Hydroxyl-Isochromanones and -Isobenzofuranones: Concise Synthesis of the Isochromanone Core of the Ajudazols

  摘要：

  An efficient synthetic strategy to access hydroxyl-isochromanone and -isobenzofurans from readily available joint alkene precursors by a regiodivergent one-pot iodocyclization-substitution tandem process is reported. The cyclizations proceed with excellent diastereoselectivities, with E-alkenes giving syn-configured products and Z-alkenes giving anti-products. A strong influence of light on the regioselectivity of the reaction was observed. High yields were also observed under radical conditions. The protective-group-free method enables a highly concise synthesis of the authentic isochromanone core of the ajudazols, which are highly potent inhibitors of the mitochondrial respiratory chain.

  DOI：

  10.1055/s-0035-1561278
• 作为产物：
  描述：

  1-戊炔 、 频那醇硼烷 在 chloro(1,5-cyclooctadiene)rhodium(I) dimer 、 三乙胺 、 tricyclohexylphosphine tetrafluoroborate 作用下， 以 环己烷 为溶剂， 反应 5.0h， 以50%的产率得到(Z)-4,4,5,5-tetramethyl-2-(pent-1-enyl)-1,3,2-dioxaborolane
  参考文献：
  名称：

  铑催化的1-烯基硼酸酯与醛的醛化反应生成烯丙基化产物

  摘要：

  合成等效物：1-烯基硼酸酯起烯丙基化试剂的作用。它们在阳离子铑（I）/ dppm催化剂存在下与醛的反应导致非构型高选择性生成反构型均烯丙基醇（参见方案; Bpin = 4、4、5、5-四甲基-1,3,2 -二氧杂硼硼烷基）。

  DOI：

  10.1002/anie.201105148

文献信息

• Isonicotinate Ester Catalyzed Decarboxylative Borylation of (Hetero)Aryl and Alkenyl Carboxylic Acids through <i>N</i>-Hydroxyphthalimide Esters
  作者：Wan-Min Cheng、Rui Shang、Bin Zhao、Wei-Long Xing、Yao Fu

  DOI：10.1021/acs.orglett.7b01950

  日期：2017.8.18

  Decarboxylative borylation of aryl and alkenyl carboxylic acids with bis(pinacolato)diboron was achieved through N-hydroxyphthalimide esters using tert-butyl isonicotinate as a catalyst under base-free conditions. A variety of aryl carboxylic acids possessing different functional groups and electronic properties can be smoothly converted to aryl boronate esters, including those that are difficult to

  芳基和链烯基羧酸与双（频哪醇合）二硼的脱羧硼化通过实现Ñ使用-hydroxyphthalimide酯叔异烟酸丁酯在无碱条件下作为催化剂。可以将具有不同官能团和电子特性的各种芳基羧酸平稳地转化为芳基硼酸酯，包括在过渡金属催化下难以脱羧的芳基硼酸酯，从而提供了一种新方法，使羧酸可以用作有机合成中的基础。机理分析表明，该反应通过自由基脱羧产生的瞬态芳基与吡啶稳定的持久性硼基的偶联而进行。氧化还原活性酯的活化可以通过分子内单电子转移（SET）过程，通过吡啶-二硼-邻苯二甲酰亚胺加合物进行，并说明了无碱反应条件。
• Rhodium-Catalyzed Dehydrogenative Borylation of Aliphatic Terminal Alkenes with Pinacolborane
  作者：Masao Morimoto、Tomoya Miura、Masahiro Murakami

  DOI：10.1002/anie.201506328

  日期：2015.10.19

  Aliphatic terminal alkenes react with pinacolborane at ambient temperature to afford dehydrogenative borylation compounds as the major product when iPr‐Foxap is used as the ligand with cationic rhodium(I) in the presence of norbornene, which acts as the sacrificial hydrogen acceptor. The reaction is applied to the one‐pot syntheses of aldehydes and homoallylic alcohols from aliphatic terminal alkenes

  当i Pr-Foxap在降冰片烯的存在下用作阳离子铑（I）的配体时，脂族末端烯烃在室温下与频哪醇硼烷反应，以脱氢硼化化合物为主要产物，后者是牺牲氢受体。该反应适用于由脂肪族末端烯烃单醛合成醛和均烯丙基醇。
• Catalytic Non-Conventional trans-Hydroboration: A Theoretical and Experimental Perspective
  作者：Jessica Cid、Jorge J. Carbó、Elena Fernández

  DOI：10.1002/chem.201102729

  日期：2012.1.27

  four stages: 1) isomerization of the alkyne into the vinylidene, 2) oxidative addition of the borane reagent, 3) vinylidene insertion into the RhH bond, and finally 4) reductive elimination of the CB bond to yield the 1‐alkenylboronate. Calculations indicated that the vinylidene insertion is the selectivity‐determining step. This result was consistent with the observed Z selectivity when the sterically

  我们已经在实验和理论上研究了炔烃的非常规反式-硼氢化反应。基于[Rh（cod）Cl} 2 ] / PCy 3（cod = 1,5-环辛二烯，Cy = cyclohexyl）的原位混合物的催化体系能够活化频哪醇硼烷和儿茶酚硼烷并转移硼烷基和氢化物基团在末端炔烃的相同的不受阻碍的碳原子上。与传统的顺式硼氢化相比，碱（Et 3 N）的存在有利于非常规的反式硼氢化。改变底物对反应有显着影响，对位观察到高达99％的转化率和94％的区域选择性甲基苯基乙炔 DFT和量子力学/分子机械的ONIOM计算都是在[RhCl（PR 3）2 ]系统上进行的。为了解释对（Z）-烯基硼酸酯的选择性，我们使用丙炔作为模型炔，探索了传统顺式氢硼化的几种替代机理。所提出的机理可分为四个阶段：1）炔烃异构化为亚乙烯基，2）氧化加入硼烷试剂，3）亚乙烯基插入RhH键，最后4）还原消除CB键产生1-烯基硼酸酯。计算表明，亚乙
• Regiodivergent Iodocyclizations for the Highly Diastereoselective Synthesis of syn- and anti-Hydroxyl-Isochromanones and -Isobenzofuranones: Concise Synthesis of the Isochromanone Core of the Ajudazols
  作者：Dirk Menche、Sebastian Thiede、Peter Winterscheid、Jan Hartmann、Gregor Schnakenburg、Sebastian Essig

  DOI：10.1055/s-0035-1561278

  日期：——

  An efficient synthetic strategy to access hydroxyl-isochromanone and -isobenzofurans from readily available joint alkene precursors by a regiodivergent one-pot iodocyclization-substitution tandem process is reported. The cyclizations proceed with excellent diastereoselectivities, with E-alkenes giving syn-configured products and Z-alkenes giving anti-products. A strong influence of light on the regioselectivity of the reaction was observed. High yields were also observed under radical conditions. The protective-group-free method enables a highly concise synthesis of the authentic isochromanone core of the ajudazols, which are highly potent inhibitors of the mitochondrial respiratory chain.
• Rhodium-Catalyzed Reaction of 1-Alkenylboronates with Aldehydes Leading to Allylation Products
  作者：Hiroshi Shimizu、Tomohiro Igarashi、Tomoya Miura、Masahiro Murakami

  DOI：10.1002/anie.201105148

  日期：2011.11.25

  Synthetic equivalents: 1‐Alkenylboronates perform the role of an allylating reagent. Their reaction with aldehydes in the presence of a cationic rhodium(I)/dppm catalyst results in a highly diastereoselective production of anti‐configured homoallylic alcohols (see scheme; Bpin=4,4,5,5‐tetramethyl‐1,3,2‐dioxaborolanyl).

  合成等效物：1-烯基硼酸酯起烯丙基化试剂的作用。它们在阳离子铑（I）/ dppm催化剂存在下与醛的反应导致非构型高选择性生成反构型均烯丙基醇（参见方案; Bpin = 4、4、5、5-四甲基-1,3,2 -二氧杂硼硼烷基）。