(E)-2-(2-(benzo[d][1,3]dioxol-5-yl)vinyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane | 1618099-57-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并间二氧杂环戊烯类
• 英文名称: (E)-2-(2-(benzo[d][1,3]dioxol-5-yl)vinyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
• 英文别名: 2-[(E)-2-(1,3-benzodioxol-5-yl)ethenyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
• CAS: 1618099-57-2
• 化学式: C₁₅H₁₉BO₄
• 分子量: 274.124
• InChiKey: NTZLQYRFRIWXQZ-BQYQJAHWSA-N

物化性质

• 沸点：
  324.7±52.0 °C(Predicted)
• 密度：
  1.14±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.06
• 重原子数：
  20
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  36.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (E)-2-(2-(benzo[d][1,3]dioxol-5-yl)vinyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 在 吡啶 、 sodium tetrahydroborate 、 sodium periodate 、 sodium perborate tetrahydrate 、 二苯基膦叠氮化物 、 水 、 氯化铵 、 对甲苯磺酸 、 三乙胺 、 间氯过氧苯甲酸 、 三苯基膦 、 三氟乙酸 、 lithium hydroxide 、 锌 、 偶氮二甲酸二乙酯 作用下， 以 四氢呋喃 、 5,5-dimethyl-1,3-cyclohexadiene 、 乙醇 、 二氯甲烷 、 水 、 1,2-二氯乙烷 、 甲苯 为溶剂， 反应 328.63h， 生成 5-oxo-2,3a1,4,5,7,12b-hexahydro-1H-[1,3]dioxolo[4,5-j]pyrrolo[3,2,1-de]-phenanthridine-1,2-diyl diacetate
  参考文献：
  名称：

  Total Synthesis of (±)-Lycorine from the Endo-Cycloadduct of 3,5-Dibromo-2-pyrone and (E)-β-Borylstyrene

  摘要：

  A new synthetic route to (+/-)-lycorine, starting from the endo-cycloadduct of 3,5-dibromo-2-pyrone and (E)-beta-borylstyrene, is reported. Boronate oxidation and a set of reactions including face-selective epoxidation provided the pivotal C1-OH group and C3/C3a double bond.

  DOI：

  10.1021/ol502792p
• 作为产物：
  描述：

  5-乙炔苯并[1,3]间二氧杂环戊烯 、 频那醇硼烷 在 Schwartz's reagent 作用下， 以 二氯甲烷 为溶剂， 反应 24.0h， 以85%的产率得到(E)-2-(2-(benzo[d][1,3]dioxol-5-yl)vinyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
  参考文献：
  名称：

  Total Synthesis of (±)-Lycorine from the Endo-Cycloadduct of 3,5-Dibromo-2-pyrone and (E)-β-Borylstyrene

  摘要：

  A new synthetic route to (+/-)-lycorine, starting from the endo-cycloadduct of 3,5-dibromo-2-pyrone and (E)-beta-borylstyrene, is reported. Boronate oxidation and a set of reactions including face-selective epoxidation provided the pivotal C1-OH group and C3/C3a double bond.

  DOI：

  10.1021/ol502792p

文献信息

• Enantioselective Conjunctive Cross-Coupling of Bis(alkenyl)borates: A General Synthesis of Chiral Allylboron Reagents
  作者：Emma K. Edelstein、Sheila Namirembe、James P. Morken

  DOI：10.1021/jacs.7b01774

  日期：2017.4.12

  conjunctive cross-coupling is used for the synthesis of enantioenriched allylboron reagents. This reaction employs nonsymmetric bis(alkenyl)borates as substrates and appears to occur by a mechanism that involves selective activation of the less substituted alkene followed by migration of the more substituted alkene during the course of a Pd-induced metalate rearrangement.

  钯催化的连接交叉偶联用于合成富含对映体的烯丙基硼试剂。该反应使用非对称双（烯基）硼酸盐作为底物，似乎通过一种机制发生，该机制涉及选择性活化较少取代的烯烃，然后在 Pd 诱导的金属酸盐重排过程中迁移较多取代的烯烃。
• Rhodium-Catalyzed Deoxygenation and Borylation of Ketones: A Combined Experimental and Theoretical Investigation
  作者：Lei Tao、Xueying Guo、Jie Li、Ruoling Li、Zhenyang Lin、Wanxiang Zhao

  DOI：10.1021/jacs.0c07854

  日期：2020.10.21

  The rhodium-catalyzed deoxygenation and borylation of ketones with B2pin2 have been developed, leading to efficient formation of alkenes, vinylboronates, and vinyldiboronates. These reactions feature mild reaction conditions, a broad substrate scope, and excellent functional-group compatibility. Mechanistic studies support that the ketones initially undergo a Rh-catalyzed deoxygenation to give alkenes

  已经开发了铑催化的酮与 B2pin2 的脱氧和硼酸化，从而有效地形成烯烃、乙烯基硼酸酯和乙烯基二硼酸酯。这些反应的特点是反应条件温和，底物范围广，官能团兼容性好。机理研究支持酮最初经过 Rh 催化脱氧以通过硼烯醇化物中间体得到烯烃，随后 Rh 催化的烯烃脱氢硼化导致乙烯基硼酸酯和二硼化产物的形成，这也得到 DFT 计算的支持。
• Copper-catalyzed Decarboxylative Hydroboration: Synthesis of Vinyl Boronic Esters
  作者：Francis Mariaraj Irudayanathan、Gabriel Charles Edwin Raja、Han-Sung Kim、Kyungsu Na、Sunwoo Lee

  DOI：10.1002/bkcs.10706

  日期：2016.4

  Vinyl boronic esters were synthesized from aryl alkynyl carboxylic acids and bis(pinacolato)diboron using a copper‐catalyzed decarboxylative reaction. The reaction was conducted with CuI (10 mol%), bis‐[2‐(diphenylphosphino)phenyl]ether(20 mol%), and LiOMe (20 mol%) in DMSO at 50 °C for 16 h. This method provided the desired vinyl boronic esters in good‐to‐moderate yields and showed good functional

  乙烯基硼酸酯是通过铜催化的脱羧反应由芳基炔基羧酸和双（频哪醇）二硼合成的。反应是在50°C下于DMSO中使用CuI（10 mol％），双[2-（二苯基膦基）苯基]醚（20 mol％）和LiOMe（20 mol％）进行的。该方法以中等至中等的收率提供了所需的乙烯基硼酸酯，并显示出良好的官能团耐受性。
• Ruthenium-Catalyzed One-Pot Synthesis of (<i>E</i>)-(2-Arylvinyl)boronates through an Isomerization/Cross-Metathesis Sequence from Allyl-Substituted Aromatics
  作者：Rémy Hemelaere、Frédéric Caijo、Marc Mauduit、François Carreaux、Bertrand Carboni

  DOI：10.1002/ejoc.201402192

  日期：2014.6

  We described the efficient preparation of (E)-(2-arylvinyl)boronates from allylbenzene derivatives on the basis of an isomerization/cross-metathesis sequence catalyzed by a modified Hoveyda–Grubbs catalyst. The implementation of the experimental procedure was simple and compatible with a large variety of substrates. This methodology provides a new chemical transformation not described to date. Allyl-substituted

  我们描述了基于由改进的 Hoveyda-Grubbs 催化剂催化的异构化/交叉复分解序列，从烯丙基苯衍生物有效制备 (E)-(2-芳基乙烯基)硼酸酯。实验程序的实施很简单，并且与多种基材兼容。该方法提供了迄今为止未描述的新化学转化。因此，烯丙基取代的芳烃只需两个步骤即可转化为多种功能化的化合物，例如 (E)-二苯乙烯衍生物或 (E)-乙烯基叠氮化物。
• Cu-Catalyzed Stereoselective Borylation of <i>gem</i>-Difluoroalkenes with B₂pin₂
  作者：Juan Zhang、Wenpeng Dai、Qingyun Liu、Song Cao

  DOI：10.1021/acs.orglett.7b01430

  日期：2017.6.16

  A novel and efficient method for the synthesis of (Z)-fluorinated alkenylboronic acid pinacol esters via Cu-catalyzed stereoselective borylation of gem-difluoroalkenes using bis(pinacolato)diboron (B2pin2) as the boron source with the assistance of NaOtBu and Xantphos at room temperature was developed.

  一种新的高效方法，以双（频哪醇）二硼烷（B 2 pin 2）为硼源，在NaO t的辅助下，通过Cu催化的宝石-二氟烯烃立体选择性硼化来合成（Z）氟代烯基硼酸频哪醇酯。开发了室温下的Bu和Xantphos。