3-bromo-5-iodophenyl boronic acid pinacol ester | 942069-57-0

• 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: 3-bromo-5-iodophenyl boronic acid pinacol ester
• 英文别名: 2-(3-Bromo-5-iodophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
• CAS: 942069-57-0
• 化学式: C₁₂H₁₅BBrIO₂
• 分子量: 408.869
• InChiKey: VWSLBDHHWQNXEW-UHFFFAOYSA-N

物化性质

• 沸点：
  401.9±40.0 °C(Predicted)
• 密度：
  1.72±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.35
• 重原子数：
  17
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 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：

  3-bromo-5-iodophenyl boronic acid pinacol ester 在 Oxone 作用下， 以 丙酮 为溶剂， 反应 0.12h， 生成 3-溴-5-碘苯酚
  参考文献：
  名称：

  C−H Activation/Borylation/Oxidation:  A One-Pot Unified Route To Meta-Substituted Phenols Bearing Ortho-/Para-Directing Groups

  摘要：

  An efficient one-pot C-H activation/borylation/oxidation protocol for the preparation of phenols is described. This method is particularly attractive for the generation of meta-substituted phenols bearing ortho-/para-directing groups, as such substrates are difficult to access by other phenol syntheses.

  DOI：

  10.1021/ja0349857
• 作为产物：
  描述：

  1-溴-3-碘苯 、 联硼酸频那醇酯 在 [Ir(OMe)(COD)]2 、 4,4'-二叔丁基-2,2'-二吡啶 作用下， 以 正己烷 为溶剂， 反应 11.0h， 生成 3-bromo-5-iodophenyl boronic acid pinacol ester
  参考文献：
  名称：

  Process for the synthesis of phenols from arenes

  摘要：

  描述了一种合成取代酚的过程，如通式RR′R″Ar(OH)中的那些，其中R、R′和R″分别独立地是氢或不干扰合成取代酚过程的任何基团，包括但不限于卤素、烷基、烷氧基、羧酸酯、胺、酰胺；Ar是芳基或杂芳基的任何种类，通过氧化取代芳基硼酸酯来实现。具体地，描述了一种金属催化的C—H活化/硼化反应，随后在单个或分离的反应容器中直接氧化，从而获得酚，无需任何中间操作。更具体地，描述了一种通过Ir催化的芳烃硼化反应，使用二醇硼烷（HBPin）后，通过OXONE氧化中间芳基硼酸酯的过程。

  公开号：

  US20040030197A1

文献信息

• Metal-organic frameworks containing nitrogen-donor ligands for efficient catalytic organic transformations
  申请人：The University of Chicago

  公开号：US10647733B2

  公开（公告）日：2020-05-12

  Metal-organic framework (MOFs) compositions based on nitrogen donor-based organic bridging ligands, including ligands based on 1,3-diketimine (NacNac), bipyridines and salicylaldimine, were synthesized and then post-synthetically metalated with metal precursors, such as complexes of first row transition metals. Metal complexes of the organic bridging ligands could also be directly incorporated into the MOFs. The MOFs provide a versatile family of recyclable and reusable single-site solid catalysts for catalyzing a variety of asymmetric organic transformations. The solid catalysts can also be integrated into a flow reactor or a supercritical fluid reactor.

  基于以氮为供体的有机桥联配体，包括基于1,3-二酮亚胺（NacNac）、联吡啶和柳酸亚胺的金属-有机框架（MOFs）组成物被合成，然后用金属前驱体如第一行过渡金属的络合物进行后合成金属化。有机桥联配体的金属络合物也可以直接并入MOFs中。MOFs提供了一个多功能的、可回收和可重复使用的单点固体催化剂家族，用于催化各种不对称有机转化。这些固体催化剂也可以集成到流动反应器或超临界流体反应器中。
• Zirconaaziridine-Mediated Ni-Catalyzed Diastereoselective C(sp2)-Glycosylation
  作者：Yu Gan、Jun-Feng Zhou、Xuejiao Li、Ji-Ren Liu、Fang-Jie Liu、Xin Hong、Baihua Ye

  DOI：10.1021/jacs.4c04587

  日期：2024.6.19

  catalysis, enabling the diastereoselective coupling of bench-stable glycosyl phosphates with a range of (hetero)aromatic and glycal iodides as feasible coupling electrophiles. Our developed method showcases a broad scope and a high tolerance for various functional groups. More importantly, precise stereocontrol toward both anomeric configurations of forming C(sp2)-glycosides can be realized by simply utilizing

  在有机合成领域，C-糖苷键的催化和立体选择性形成是连接碳水化合物和糖苷配基的关键过程。然而，糖支架的固有手性通常对手性配体施加的立体诱导具有重大影响。在这项研究中，我们建立了一种前所未有的锆氮丙啶介导的不对称镍催化作用，使得稳定的糖基磷酸酯与一系列（杂）芳香族和糖醛碘化物作为可行的亲电试剂进行非对映选择性偶联。我们开发的方法展示了广泛的范围和对各种官能团的高耐受性。更重要的是，通过在这种还原镍催化中简单地利用流行的手性二恶唑啉（biOx）配体，可以实现对形成C（sp 2 ）-糖苷的两种异头构型的精确立体控制。关于操作机制，实验和计算研究都支持氧化还原金属转移过程的发生，导致瞬态双金属 Ni-Zr 物质的形成，在催化过程中充当有效且高效的单电子还原剂。
• Harnessing C–H Borylation/Deborylation for Selective Deuteration, Synthesis of Boronate Esters, and Late Stage Functionalization
  作者：Venkata A Kallepalli、Kristin A. Gore、Feng Shi、Luis Sanchez、Ghayoor A. Chotana、Susanne L. Miller、Robert E. Maleczka、Milton R. Smith

  DOI：10.1021/acs.joc.5b01588

  日期：2015.8.21

  Ir-catalyzed deborylation can be used to selectively deuterate aromatic and heteroaromatic substrates. Combined with the selectivities of Ir-catalyzed C-H borylations, uniquely labeled compounds can be prepared. In addition, diborylation/deborylation reactions provide monoborylated regioisomers that complement those prepared by C-H borylation. Comparisons between Ir-catalyzed deborylations and Pd-catalyzed deborylations of diborylated indoles described by Movassaghi are made. The Ir-catalyzed process is more effective for deborylating aromatics and is generally more effective in the monodeborylation of diborylated thiophenes. These processes can be applied to complex molecules such as dopidogrel.
• Postsynthetic Metalation of Bipyridyl-Containing Metal–Organic Frameworks for Highly Efficient Catalytic Organic Transformations
  作者：Kuntal Manna、Teng Zhang、Wenbin Lin

  DOI：10.1021/ja5018267

  日期：2014.5.7

  We have designed highly stable and recyclable single-site solid catalysts via postsynthetic metalation of the 2,2'-bipyridyl-derived metal organic framework (MOF) of the UiO structure (bpy-UiO). The Ir-functionalized MOF (bpy-UiO-Ir) is a highly active catalyst for both borylation of aromatic C-H bonds using B-2(pin)(2) (pin = pinacolate) and ortho-silylation of benzylicsilyl ethers; the ortho-silylation activity of the bpy-UiO-Ir is at least 3 orders of magnitude higher than that of the homogeneous control. The Pd-functionalized MOF (bpy-UiO-Pd) catalyzes the dehydrogenation of substituted cyclohexenones to afford phenol derivatives with oxygen as the oxidant. Most impressively, the bpy-UiO-Ir was recycled and reused 20 times for the borylation reaction without loss of catalytic activity or MOF crystallinity. This work highlights the opportunity in designing highly stable and active catalysts based on MOFs containing nitrogen donor ligands for important organic transformations.