4,4,5,5-tetramethyl-2-(1-vinylcyclohexyl)-1,3,2-dioxaborolane | 1607854-61-4

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 硼酸衍生物
• 英文名称: 4,4,5,5-tetramethyl-2-(1-vinylcyclohexyl)-1,3,2-dioxaborolane
• CAS: 1607854-61-4
• 化学式: C₁₄H₂₅BO₂
• 分子量: 236.162
• InChiKey: VLTQPXGESRJEGQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.97
• 重原子数：
  17.0
• 可旋转键数：
  2.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.86
• 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：

  肉桂基氯 、 4,4,5,5-tetramethyl-2-(1-vinylcyclohexyl)-1,3,2-dioxaborolane 在 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 为溶剂， 反应 14.0h， 以85%的产率得到(R)-(1-(1-vinylcyclohexyl)allyl)benzene
  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：

  环己酮 在 氯化亚砜 、 magnesium 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 8.0h， 生成 4,4,5,5-tetramethyl-2-(1-vinylcyclohexyl)-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

• Allylboronic Esters as Acceptors in Radical Addition, Boron 1,2-Migration, and Trapping Cascades
  作者：Kalipada Jana、Armido Studer

  DOI：10.1021/acs.orglett.2c00039

  日期：2022.2.4

  Radical 1,3-carboheteroarylation and 1,3-hydroalkylation of allylboronic esters comprising a 1,2-boron shift is reported. Allylboronic esters are generally used in synthesis as allylation reagents, where the boronic ester moiety gets lost. In the introduced cascades, alkylboronic esters are obtained with the boron entity remaining in the product. The carboheteroarylation of the allylboronic esters

  报道了包含 1,2-硼位移的烯丙基硼酸酯的自由基 1,3-碳杂芳基化和 1,3-氢化烷基化。烯丙基硼酸酯通常在合成中用作烯丙基化试剂，其中硼酸酯部分会丢失。在引入的级联中，得到烷基硼酸酯，而硼实体保留在产物中。烯丙基硼酸酯的碳杂芳基化是在没有金属催化剂的情况下进行的，而 1,3-氢化烷基化是使用铁催化实现的。这两种反应都在温和条件下有效地进行。
• Photocatalyzed Radical Relayed Regio- and Stereoselective Trifluoromethylthiolation–Boration
  作者：Qiang Zhang、Xiaojuan Li、Weigang Zhang、Yi Wang、Yi Pan

  DOI：10.1021/acs.orglett.1c01737

  日期：2021.7.16

  sequential radical difunctionalization strategy for the construction of fluorine-containing vinylboronates and alkylboronates with the integrated redox-active reagent N-trifluoromethylthiophthalimide. This multifunctional N–S precursor offers a scalable and practical protocol for the trifluoromethylthiolation–borylation of unsaturated hydrocarbons in a highly regio- and stereoselective fashion, which

  乙烯基硼酸酯和烷基硼酸酯是化学科学各个方面的杂色转化的关键组成部分。这项工作描述了一种用于构建含氟乙烯基硼酸酯和烷基硼酸酯的连续自由基双官能化策略，其中包含集成的氧化还原活性试剂N-三氟甲基硫代邻苯二甲酰亚胺。这种多功能 N-S 前体以高度区域和立体选择性的方式为不饱和烃的三氟甲基硫醇化-硼酸化提供了一种可扩展且实用的方案，可通过硼基迁移进一步转化为有价值的合成子。
• 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。