2,2'-(3-(2-bromophenyl)propane-1,1-diyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) | 1512864-22-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2,2'-(3-(2-bromophenyl)propane-1,1-diyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane)
• CAS: 1512864-22-0
• 化学式: C₂₁H₃₃B₂BrO₄
• 分子量: 451.017
• InChiKey: LHSAOQXXPXCNNH-UHFFFAOYSA-N

物化性质

• 熔点：
  80-82 °C
• 沸点：
  448.9±45.0 °C(predicted)
• 密度：
  1.18±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.48
• 重原子数：
  28.0
• 可旋转键数：
  5.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  36.92
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  2,2'-(3-(2-bromophenyl)propane-1,1-diyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) 在 2,2,6,6-tetramethylpiperidinyl-lithium 、 palladium diacetate 、 N,N-二异丙基乙胺 、 4,5-双二苯基膦-9,9-二甲基氧杂蒽 作用下， 以 四氢呋喃 为溶剂， 反应 5.17h， 生成 anti-3-(2-bromophenethyl)-5,6-diphenyl-5,6-dihydro-2H-1,2-oxaborinin-2-ol
  参考文献：
  名称：

  Palladium‐Catalyzed Cascade Heck Coupling and Allylboration of Iododiboron Compounds via Diboryl Radicals

  摘要：

  Geminal bis(boronates) are versatile synthetic building blocks in organic chemistry. The fact that they predominantly serve as nucleophiles in the previous reports, however, has restrained their synthetic potential. Herein we disclose the ambiphilic reactivity of α‐halogenated geminal bis(boronates), of which the first catalytic utilization was accomplished by merging a formal Heck cross‐coupling with a highly diastereoselective allylboration of aldehydes or imines, providing a new avenue for rapid assembly of polyfunctionalized boron‐containing compounds. We demonstrated that this cascade reaction is highly efficient and compatible with various functional groups, and a wide range of heterocycles. In contrast to a classical Pd(0/II) scenario, mechanistic experiments and DFT calculations have provided strong evidence for a catalytic cycle involving Pd(I)/diboryl carbon radical intermediates.

  DOI：

  10.1002/anie.202401050
• 作为产物：
  描述：

  联硼酸频那醇酯 在 [Ir(dF(CF₃)ppy)₂(dtbbpy)](PF₆) 、 cesium fluoride 作用下， 以 乙醚 、 N,N-二甲基乙酰胺 、 正戊烷 为溶剂， -110.0~30.0 ℃ 、101.33 kPa 条件下， 反应 24.67h， 生成 2,2'-(3-(2-bromophenyl)propane-1,1-diyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane)
  参考文献：
  名称：

  宝石-二硼烷基烯烃的光氧化还原介导的反应：对不同的1,1-双硼烷基烷烃的反应性。

  摘要：

  首次探索了将宝石-二硼烷基烯烃用作自由基反应基团。这些反应提供了一种有效且通用的方法，用于宝石-二硼烷基烯烃的光化学转化，以快速获得1,1-双硼烷基烷烃。该方法利用了一种新的光氧化还原脱羧基团加到宝石-二硼烷基烯烃上，得到α-宝石-二硼基碳中心自由基，该自由基由于与硼上的空p-轨道相互作用而得益于额外的稳定性。该反应为γ-氨基宝石-二硼烷基烷烃提供了高度模块化和区域选择性的方法。此外，EPR光谱和DFT计算分别提供了对光化学反应和双金属化自由基稳定性的潜在自由基机理的了解。

  DOI：

  10.1002/chem.202000603

文献信息

• Stereoselective Desymmetrization of <i>gem</i> ‐Diborylalkanes by “Trifluorination”
  作者：Nivesh Kumar、Reddy Rajasekhar Reddy、Ahmad Masarwa

  DOI：10.1002/chem.201901267

  日期：2019.6.18

  An efficient and general method for the chemoselective synthesis of unsymmetrical gem‐diborylalkanes is reported. This method is based on a late‐stage desymmetrization through nucleophilic “trifluorination”, providing chiral gem‐diborylalkanes bearing a trifluoroborate group. The reaction offers a highly modular and diastereoselective approach towards the synthesis of gem‐diborylcyclopropanes. The

  报道了一种不对称的宝石-二硼烷基烷烃化学选择性合成的有效且通用的方法。该方法基于通过亲核“三氟化”的后期去对称，提供带有三氟硼酸酯基团的手性宝石-二硼烷基烷烃。该反应为宝石-二硼烷基环丙烷的合成提供了高度模块化和非对映选择性的方法。通过对三氟硼酸酯基团的选择性后官能化，证明了宝石-二硼烷基烷烃构件的实用性。这些功能化包括内部和内部Pd催化的Suzuki-Miyaura偶联反应。
• Facile Access to Cyclopropylboronates via Stereospecific Deborylative Cyclization: A Leaving Group‐Assisted Activation of Geminal Diborons
  作者：Xin-Yi Chen、Feng-Chen Gao、Peng-Fei Ning、Yi Wei、Kai Hong

  DOI：10.1002/anie.202302638

  日期：——

  A transition metal-free deborylative cyclization strategy led to the efficient synthesis of racemic and enantioenriched cyclopropylboronates. The cyclization of geminal-bis(boronates) bearing a leaving group was highly diastereoselective and stereospecific, tolerating various functional groups and heterocycles. Mechanistic studies indicated that the leaving group at the γ-position significantly promoted

  无过渡金属的脱硼环化策略导致外消旋和对映体富集的环丙基硼酸酯的有效合成。带有离去基团的双（硼酸盐）环化具有高度的非对映选择性和立体特异性，可耐受各种官能团和杂环。机理研究表明， γ-位的离去基团显着促进了宝石-二硼部分的活化。
• Formal Carbon Insertion of <i>N-</i>Tosylhydrazone into B–B and B–Si Bonds: <i>gem</i>-Diborylation and <i>gem</i>-Silylborylation of sp³ Carbon
  作者：Huan Li、Xianghang Shangguan、Zhikun Zhang、Shan Huang、Yan Zhang、Jianbo Wang

  DOI：10.1021/ol403338s

  日期：2014.1.17

  A convenient method is developed to synthesize 1,1-diboronates from the corresponding N-tosylhydrazones. This method is also applicable to synthesize 1-silyl-1-boron compounds. Meanwhile, derivatization and consecutive Pd-catalyzed cross-coupling reactions with 1,1-boronates were explored, demonstrating the synthetic potential of 1,1-diboronates.