2-(3,7-dimethylocta-1,6-dien-3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane | 1174918-99-0

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 2-(3,7-dimethylocta-1,6-dien-3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
• CAS: 1174918-99-0
• 化学式: C₁₆H₂₉BO₂
• 分子量: 264.216
• InChiKey: QZUNBORUNCXZEN-INIZCTEOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.77
• 重原子数：
  19.0
• 可旋转键数：
  5.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  18.46
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  2-(3,7-dimethylocta-1,6-dien-3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 在 Hoveyda-Grubbs catalyst second generation 、 二氯[（R）-（+）-2,2''-双（二-2-呋喃基膦基）-6,6''-二甲氧基-1,1''-联苯]钯（II） 、 cesium fluoride 作用下， 以 四氢呋喃 、 苯 为溶剂， 反应 34.0h， 生成 (1R,2R)-2-methyl-2-vinyl-1,2,3,4-tetrahydro-1,1'-biphenyl
  参考文献：
  名称：

  Congested C–C Bonds by Pd-Catalyzed Enantioselective Allyl–Allyl Cross-Coupling, a Mechanism-Guided Solution

  摘要：

  Under the influence of a chiral bidentate diphosphine ligand, the Pd-catalyzed asymmetric cross-coupling of allylboron reagents and allylic electrophiles establishes 1,5-dienes with adjacent stereocenters in high regio- and stereoselectivity. A mechanistic study of the coupling utilizing reaction calorimetry and density functional theory analysis suggests that the reaction operates through an inner-sphere 3,3'-reductive elimination pathway, which is both rate-defining and stereodefining. Coupled with optimized reaction conditions, this mechanistic detail is used to expand the scope of allyl allyl couplings to allow the generation of 1,5-dienes with tertiary centers adjacent to quaternary centers as well as a unique set of cyclic structures.

  DOI：

  10.1021/ja502280w
• 作为产物：
  描述：

  香叶基氯 、 频那醇硼烷 在 magnesium 作用下， 以 四氢呋喃 为溶剂， 反应 4.0h， 以87%的产率得到2-(3,7-dimethylocta-1,6-dien-3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
  参考文献：
  名称：

  Congested C–C Bonds by Pd-Catalyzed Enantioselective Allyl–Allyl Cross-Coupling, a Mechanism-Guided Solution

  摘要：

  Under the influence of a chiral bidentate diphosphine ligand, the Pd-catalyzed asymmetric cross-coupling of allylboron reagents and allylic electrophiles establishes 1,5-dienes with adjacent stereocenters in high regio- and stereoselectivity. A mechanistic study of the coupling utilizing reaction calorimetry and density functional theory analysis suggests that the reaction operates through an inner-sphere 3,3'-reductive elimination pathway, which is both rate-defining and stereodefining. Coupled with optimized reaction conditions, this mechanistic detail is used to expand the scope of allyl allyl couplings to allow the generation of 1,5-dienes with tertiary centers adjacent to quaternary centers as well as a unique set of cyclic structures.

  DOI：

  10.1021/ja502280w

文献信息

• Nickel-catalyzed allyl–allyl coupling reactions between 1,3-dienes and allylboronates
  作者：Ding-Wei Ji、Gu-Cheng He、Wei-Song Zhang、Chao-Yang Zhao、Yan-Cheng Hu、Qing-An Chen

  DOI：10.1039/d0cc02697b

  日期：——

  A regiospecific allyl–allyl coupling reaction between 1,3-dienes and allylboronates has been demonstrated under nickel catalysis. Salient features of this method include the earth-abundant metal catalyst, excellent regioselectivity and good functional group tolerance. Notably, even congested allyl substrates can also be applied to this protocol, thus allowing for the rapid preparation of a series of

  在镍催化下，已经证明了1，3-二烯和烯丙基硼酸酯之间的区域特异性烯丙基-烯丙基偶联反应。该方法的显着特征包括富含稀土的金属催化剂，优异的区域选择性和良好的官能团耐受性。值得注意的是，即使拥挤的烯丙基底物也可以应用于该方案，因此可以快速制备一系列有价值的1,5-二烯。
• Enantioselective Synthesis of Allylboronates Bearing a Tertiary or Quaternary B-Substituted Stereogenic Carbon by NHC-Cu-Catalyzed Substitution Reactions
  作者：Aikomari Guzman-Martinez、Amir H. Hoveyda

  DOI：10.1021/ja104254d

  日期：2010.8.11

  Allylic substitutions that afford alpha-substituted allylboronates bearing B-substituted tertiary or quaternary carbon stereogenic centers are presented. C-B bond-forming reactions, catalyzed by chiral bidentate Cu-NHC complexes, are performed in the presence of commercially available bis(pinacolato)diboron. Transformations proceed in high yield (up to >98%) and site selectivity (>98% S(N)2'), and

  提供带有 B 取代的叔或季碳立体中心的 α 取代的烯丙基硼酸酯的烯丙基取代。由手性双齿 Cu-NHC 配合物催化的 CB 键形成反应在市售的双（频哪醇）二硼存在下进行。转化以高产率（高达 >98%）和位点选择性（>98% S(N)2'）以及高达 >99:1 的对映体比例进行。可以使用反式或顺式二取代的烯烃；烷基-（直链和支链）和芳基-三取代的烯丙基碳酸酯用作有效的底物。带有季碳中心的烯丙基硼酸酯在空气中是稳定的，可以很容易地通过硅胶色谱法纯化；相比之下，仲烯丙基硼酸酯不能以相同的方式纯化并且稳定性明显较差。
• The Isomerization of Allylrhodium Intermediates in the Rhodium-Catalyzed Nucleophilic Allylation of Cyclic Imines
  作者：Hamish B. Hepburn、Hon Wai Lam

  DOI：10.1002/anie.201407233

  日期：2014.10.20

  Allylrhodium species generated from potassium allyltrifluoroborates can undergo isomerization by 1,4‐rhodium(I) migration to give more complex isomers, which then react with cyclic imines to provide products with up to three new stereochemical elements. High enantioselectivities are obtained using chiral diene–rhodium complexes.

  由烯丙基三氟硼酸钾产生的烯丙基铑物质可以通过 1,4-铑 (I) 迁移进行异构化，产生更复杂的异构体，然后与环状亚胺反应，提供最多具有三种新立体化学元素的产品。使用手性二烯-铑络合物可以获得高对映选择性。
• Electrochemical preparation of pinacol allylboronic esters
  作者：Julien Godeau、Christine Pintaric、Sandra Olivero、Elisabet Duñach

  DOI：10.1016/j.electacta.2009.01.015

  日期：2009.9

  electroreduction of allylic halide derivatives in the presence of pinacolborane afforded allylboronic pinacol esters with moderate to good yields (up to 86%) and high regioselectivities. The electrosynthesis was carried out in a single-compartment cell with an Al anode, in THF at room temperature and it constitutes an alternative route for the preparation of allylboronic esters under mild conditions.

  在频哪醇硼烷的存在下对烯丙基卤化物衍生物进行电还原，得到了烯丙基硼酸频哪醇酯，具有中等至良好的收率（高达86％）和较高的区域选择性。电合成是在室温下在带有THF的单室电池中，在Al阳极中进行的，它构成了在温和条件下制备烯丙基硼酸酯的另一种方法。
• Radical boron migration of allylboronic esters
  作者：Xiangzhang Tao、Shengyang Ni、Lingyu Kong、Yi Wang、Yi Pan

  DOI：10.1039/d1sc06760e

  日期：——

  A photocatalyzed 1,3-boron shift of allylboronic esters is reported. The boron atom migration through the allylic carbon skeleton proceeds via consecutive 1,2-boron migrations and Smiles-type rearrangement to furnish a variety of terminally functionalized alkyl boronates. Several types of migrating variations of heteronuclei radicals and dearomatization processes are also tolerated, allowing for further

  报道了烯丙基硼酸酯的光催化 1,3-硼位移。通过烯丙基碳骨架的硼原子迁移通过连续的 1,2-硼迁移和 Smiles 型重排进行，以提供各种末端官能化的烷基硼酸盐。异核自由基和脱芳构化过程的几种类型的迁移变化也是可以容忍的，从而允许进一步细化高度功能化的含硼框架。