2,2'-(3-(4-bromophenyl)propane-1,1-diyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) | 1512864-16-2

• 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-(4-bromophenyl)propane-1,1-diyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane)
• 英文别名: 2-[3-(4-Bromophenyl)-1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)propyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
• CAS: 1512864-16-2
• 化学式: C₂₁H₃₃B₂BrO₄
• 分子量: 451.017
• InChiKey: LTMWEWHXZSJOKT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.48
• 重原子数：
  28
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.71
• 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：

  2,2'-(3-(4-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-(4-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：

  3-(4-溴苯基)丙醛 在 sodium hydride 作用下， 以 甲醇 、 甲苯 、 mineral oil 为溶剂， 反应 13.0h， 生成 2,2'-(3-(4-bromophenyl)propane-1,1-diyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane)
  参考文献：
  名称：

  Formal Carbon Insertion of N-Tosylhydrazone into B–B and B–Si Bonds: gem-Diborylation and gem-Silylborylation of sp³ Carbon

  摘要：

  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.

  DOI：

  10.1021/ol403338s

文献信息

• Electrophilic Fluorination of Alkenes via Bora‐Wagner–Meerwein Rearrangement. Access to β‐Difluoroalkyl Boronates
  作者：Qiang Wang、Maria Biosca、Fahmi Himo、Kálmán J. Szabó

  DOI：10.1002/anie.202109461

  日期：2021.12.6

  Electrophilic fluorination of alkyl substituted vinyl-Bmida species proceeds through bora-Wagner–Meerwein type rearrangement.

  烷基取代的乙烯基-Bmida 物质的亲电氟化通过 bora-Wagner-Meerwein 型重排进行。
• Boron-Promoted Deprotonative Conjugate Addition: Geminal Diborons as Soft Pronucleophiles and Acyl Anion Equivalents
  作者：Lucia Wang、Shengjia Lin、Emmanuel Santos、Jenna Pralat、Kaylyn Spotton、Abhishek Sharma

  DOI：10.1021/acs.joc.2c00914

  日期：2022.8.5

  Conjugate addition of α-boron-stabilized carbanions is an underexplored reaction modality. Existing methods require deborylation of geminal di-/triboryl alkanes and/or the presence of additional activating groups. We report the 1,4-addition of α,α-diboryl carbanions generated via deprotonation of the corresponding geminal diborons. The methodology provided a general route to highly substituted and

  α-硼稳定碳负离子的共轭加成是一种尚未充分研究的反应方式。现有方法需要偕二硼烷/三硼烷的脱硼基化和/或存在额外的活化基团。我们报告了通过相应偕二硼的去质子化产生的α,α-二硼基碳负离子的1,4-加成。该方法提供了高度取代且合成有用的γ,γ-二硼基酮的一般路线。偕二硼作为软亲核试剂的发展也使得它们能够通过一锅串联共轭加成-氧化序列用作酰基阴离子等价物。
• 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。
• Electrooxidative Activation of B−B Bond in B ₂ cat ₂ : Access to <i>gem</i> ‐Diborylalkanes via Paired Electrolysis
  作者：Bingbing Wang、Xiangyu Zhang、Yangmin Cao、Long Zou、Xiaotian Qi、Qingquan Lu

  DOI：10.1002/anie.202218179

  日期：2023.3.27

  electrooxidation of a solvent (e.g., DMF)-ligated B2cat2 complex, whereby a solvent-stabilized boryl radical is formed via quasi-homolytic cleavage of the B−B bond in a DMF-ligated B2cat2 radical cation. Furthermore, a strategy for the electrochemical gem-diborylation of gem-bromides via paired electrolysis is developed for the first time, affording a range of versatile gem-diborylalkanes.

  该报告描述了溶剂（例如 DMF）连接的 B 2 cat 2络合物前所未有的电氧化，由此通过 DMF 连接的 B 2 cat中B−B 键的准均裂裂解形成溶剂稳定的硼基自由基2自由基阳离子。此外，首次开发了一种通过配对电解对宝石-溴化物进行电化学宝石-二硼基化的策略，提供了一系列通用的宝石-二硼基烷烃。
• A General Method to Access Sterically Encumbered Geminal Bis(boronates) via Formal Umpolung Transformation of Terminal Diboron Compounds
  作者：Peng‐Fei Ning、Yi Wei、Xin‐Yi Chen、Yi‐Fei Yang、Feng‐Chen Gao、Kai Hong

  DOI：10.1002/anie.202315232

  日期：2024.1.22

  method for accessing sterically encumbered geminal bis(boronates) was developed based on a formal umpolung strategy. The polarity inversion of the readily available 1,1-diborylalkanes allows their corresponding α-halogenated derivatives to undergo a formal substitution with a wide variety of nucleophiles to form C−C, C−O, C−S, and C−N bonds, featuring excellent tolerance to steric hindrance and functional

  基于正式的umpolung策略，开发了一种获取空间阻碍的偕双（硼酸盐）的通用方法。容易获得的 1,1-二硼基烷烃的极性反转允许其相应的 α-卤化衍生物与各种亲核试剂进行形式取代，形成 C−C、C−O、C−S 和 CN−N 键，具有对空间位阻和官能团的优异耐受性。