6-methoxydecaborane | 1282607-84-4

• 英文名称: 6-methoxydecaborane
• CAS: 1282607-84-4
• 化学式: CH₁₆B₁₀O
• 分子量: 152.247
• InChiKey: PWOOVAZMTHTRTQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为产物：
  描述：

  甲醇 、 sodium decahydro-closo-decaborate 在 三氟甲磺酸三甲基硅酯 作用下， 以 正己烷 为溶剂， 以85 %的产率得到6-methoxydecaborane
  参考文献：
  名称：

  硅离子介导的 closo-B10H102- 盐的笼开功能化

  摘要：

  stable closo -B 10 H 10 2−的笼开功能化盐是获得各种硼簇的好方法。然而，已知的介导笼开功能化的方法依赖于使用强酸，其效率低且底物范围窄。在此，开发了一种合成 6-取代的十硼烷基醚和硫化物的有效方法。该反应由三氟甲磺酸三甲基甲硅烷酯 (TMSOTf) 介导，并在室温下发生。以 65-92% 的收率获得了六种 6-取代的醚，并以 38-58% 的收率制备了五种 6-取代的硫化物。该反应具有极好的区域选择性，在所有情况下都提供了单一的 B(6) 区域异构体。硼笼的 B-H 键与甲硅烷离子之间的相互作用被认为是反应的关键因素。

  DOI：

  10.1039/d2cc04892b

文献信息

• Syntheses and Surprising Regioselectivity of 5- and 6-Substituted Decaboranyl Ethers via the Nucleophilic Attack of Alcohols on 6- and 5-Halodecaboranes
  作者：William C. Ewing、Patrick J. Carroll、Larry G. Sneddon

  DOI：10.1021/ic102544v

  日期：2011.5.2

  π-backbonding from oxygen to the cage boron. A possible substitution mechanism was computationally identified involving: (1) initial nucleophilic attack by the alcohol−oxygen at a site adjacent to the 5- or 6-halo-substituted boron, (2) movement of the terminal hydrogen at the point of attack to a bridging position, (3) formation of a 5-membered (B−O−H−Cl−B) cyclic transition state allowing the acidic

  通过醇与卤代硼硼烷的反应，可以实现新型合成的十硼烷醚的选择性合成，这些醚含有一系列在B5或B6位置取代的官能团。反应出乎意料的区域选择性，其中6-卤代十二硼烷（6-XB 10 H 13）与醇的反应产生了5-取代的十硼烷醚（5-RO-B 10 H 13），并且与5-卤代硼硼烷（5-RO-B 10 H 13） 5-XB 10 H 13）得到6个取代的十硼烷醚（6-RO-B 10 H 13），通过NMR和X射线晶体学分析证实。晶体学测定还表明，癸硼烷醚具有缩短的B-O键和明显的sp 2。氧杂化表明氧与笼状硼有明显的π反向键合。通过计算确定了一种可能的取代机理，包括：（1）醇氧在与5或6卤代硼相邻的位点发生最初的亲核攻击，（2）末端氢在攻击点处向桥接位置，（3）形成5元（B-OH-Cl-B）环状过渡态，使酸性甲醇-氢键合到卤素上，（4）释放HX，最后（5 ）将桥连的氢移动到空出的末端位置。氘标记研
• Synthesis, Structural Characterization, and Reactivity Studies of 5-CF₃SO₃-B₁₀H₁₃
  作者：Emily R. Berkeley、William C. Ewing、Patrick J. Carroll、Larry G. Sneddon

  DOI：10.1021/ic500684b

  日期：2014.5.19

  In contrast to previous reactions carried out in cyclopentane solvent at room temperature that produced 6-TfO-B10H13 (TfO = CF3SO3), the reaction of c/oso-B10H102- with a large excess of trifluoromethanesulfonic acid in the ionic liquid 1-butyl-3-methylimidazolium trifluoromethanesulfonate (bmimOTf) gave exclusively the previously unknown S-TfO-B10H13 isomer. Experimental and computational studies demonstrated that the difference in the products of the two reactions is a result of 6-TfO-B10H13 isomerizing to S-TfO-B10H13 above room temperature in bmimOTf solutions. Reactivity studies showed that 5-TfO-B10H13: (1) is deprotonated by reaction with 1,8-bis(dimethylamino)naphthalene to form the S-TfO-B10H121- anion; (2) reacts with alcohols to produce 6-RO-B10H13 boryl ethers (R = Me and 4-CH3O-C6H4); (3) undergoes olefin-hydroboration reactions to form 5-TfO-6,9-R-2-B10H11 derivatives; and (4) forms a 5-TfO-6,9-(Me2S)(2)-B10H11 adduct at its Lewis acidic 6,9-borons upon reaction with dimethylsulfide. The S-TfO-6,9-(Me2S)(2)-B10H11 adduct was also found to undergo alkyne-insertion reactions to form a range of previously unreported triflate-substituted 4-TfO-ortho-carboranes (1-R-4-TfO-1,2-C2B10H10) and reactions with triethylamine or ammonia to form the first TfO-substituted decaborate [R3NH+](2)[2-TfO-B10H92-], and [R3NH+](2)[1-TfO-B10H92-] (R = H, Et) salts.