(dimethoxy)thexyl borane | 56118-62-8

• 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: (dimethoxy)thexyl borane
• 英文别名: thexyldimethoxyborane；Dimethylthexylboranat；Boronic acid, (1,1,2-trimethylpropyl)-, dimethyl ester；2,3-dimethylbutan-2-yl(dimethoxy)borane
• CAS: 56118-62-8
• 化学式: C₈H₁₉BO₂
• 分子量: 158.049
• InChiKey: HAQMGXUOIUDZJK-UHFFFAOYSA-N

物化性质

• 沸点：
  110.6±9.0 °C(Predicted)
• 密度：
  0.807±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  11
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 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：

  N-甲基亚氨二乙酸 、 (dimethoxy)thexyl borane 以 二甲基亚砜 、 苯 为溶剂， 以50%的产率得到(N-B)thexyl[N-methyliminodiacetate-O,N]borane
  参考文献：
  名称：

  源自亚氨基二乙酸的新型双环有机基硼酸酯

  摘要：

  苯基硼酸或dinethylthexyboronic酯与iminodiacetic-或反应ñ -methyliminodiacetic酸导致高产率的空气稳定的双环酯（NB）苯基[iminodiacete- ø，Ñ ]硼烷（1），（NB）苯基[ Ñ - methyliminodiacetate- ø，ñ ]硼烷（2），（NB）thexy [亚氨基二乙酸[ ø，ñ ]硼烷（3）和（NB）叔己基[ ñ -methyliminodiacetate- ø，ñ ]硼烷（4）。这些由1 H，11 B和13表示13 C NMR光谱显示具有强分子内NB配位的刚性双环结构。

  DOI：

  10.1016/0022-328x(86)80169-3
• 作为产物：
  描述：

  thexylchloroborane*methyl sulfide 在 吡啶 、 甲醇 作用下， 以>99的产率得到(dimethoxy)thexyl borane
  参考文献：
  名称：

  Brown, Herbert C.; Sikorski, James A., Organometallics, 1982, vol. 1, # 50, p. 28 - 37

  摘要：

  DOI：

文献信息

• Thexylborane-A Highly Versatile Reagent for Organic Synthesis via Hydroboration
  作者：Ei-ichi NEGISHI、Herbert C. BROWN

  DOI：10.1055/s-1974-23248

  日期：——

  The present review discusses the chemistry of thexylborane pertinent to organic synthesis, and summarizes scattered results of organic synthesis involving thexylborane. 1.Chemistry of Thexylborane 1.1. Preparation and Characterization of Thexylborane 1.2. Reaction of Thexylborane with Olefins 2. Synthetic Applications of Thexylborane 2.1. Synthesis of Unsymmetrical Ketones - A Multi-Carbon Homologation of Olefins 2.2. Synthesis of Cyclic Ketones - A New Annelation Reaction 2.3. Coupling of Two Unlike Alkyl Groups via Bromination of Thexyldialkylboranes 2.4. Synthesis of trans-Disubstituted Olefins 2.5. Syntheses of Conjugated Dienes 2.6. Stereoselective Syntheses of Diols from Dienes 2.7. Synthesis of 1,5-Diols from Monoolefins 2.8. Synthesis of Monoalkylboranes as Triethylaminates 2.9. Selective Reduction with Thexylborane 2.10.Selective Reduction with Trialkylborohydrides Containing the Thexyl Group

  本综述讨论了与有机合成相关的那西醇硼烷的化学，并总结了涉及那西醇硼烷的有机合成的分散结果。 1. 那西醇硼烷的化学 1.1. 那西醇硼烷的制备与表征 1.2. 那西醇硼烷与烯烃的反应 2. 那西醇硼烷的合成应用 2.1. 不对称酮的合成 - 烯烃的碳链延长反应 2.2. 环状酮的合成 - 一种新的环化反应 2.3. 通过那西二烷基硼烷的溴化实现两种不同烷基的连接 2.4. 反式二取代烯烃的合成 2.5. 共轭二烯的合成 2.6. 二烯的立体选择性二醇合成 2.7. 单烯烃的1,5-二醇合成 2.8. 单烷基硼烷的合成作为三乙基胺酸盐 2.9. 那西醇硼烷的选择性还原 2.10. 含有那西基团的三烷基硼氢化物的选择性还原
• Factors Affecting Migration of Tertiary Alkyl Groups in Reactions of Alkylboronic Esters with Bromomethyllithium
  作者：Mark C. Elliott、Keith Smith、D. Heulyn Jones、Ajaz Hussain、Basil A. Saleh

  DOI：10.1021/jo4000459

  日期：2013.4.5

  be of great potential for the formation of quaternary carbon centers but often give poor yields/conversions. Calculations and experimental evidence show that tert-alkyl groups migrate less effectively than other types of alkyl group in such reactions and that O-migration competes. Furthermore, slow/incomplete capture of the bromomethyl reagent by the boronic ester is a problem in more hindered systems

  溴甲基锂与叔烷基硼酸酯的反应对于形成季碳中心可能具有巨大潜力，但通常收率/转化率很低。计算和实验证据表明，叔烷基基团比在这样的反应和其它类型的烷基的更小有效迁移ö移民竞争。此外，在更受阻的系统中，硼酸酯无法缓慢/不完全捕获溴甲基试剂是一个问题，另外的竞争性反应（可能在溴甲基硼酸酯种类上进行Li-Br交换）也会导致迁移产物的收率降低。基于此，已经设计了实验方案，其中竞争反应被大大抑制，从而导致针对多种底物的转化产物的转化率更高。
• Molecular Addition Compounds. 15. Synthesis, Hydroboration, and Reduction Studies of New, Highly Reactive <i>tert</i>-Butyldialkylamine−Borane Adducts
  作者：Herbert C. Brown、Josyula V. B. Kanth、Pramod V. Dalvi、Marek Zaidlewicz

  DOI：10.1021/jo990379b

  日期：1999.8.1

  Two series of tert-butyldialkylamines have been prepared and examined for borane complexation. The complexing ability of each amine in the two series examined decreases in the order shown. First series: t-BuN(CH2CH2)(2)O 1a > t-BuNEt2 Ib > t-BuNPr(2)(n)1c > t-BuN(CH2CH2OMe)(2) Id much greater than t-BuNBu2i le. Second series: t-(BuNBuMe)-Me-i 2a > t-(BuNPrMe)-Me-i 2b > t-(BuNBuEt)-Et-i 2c > t-(BuNBuPrn)-Pr-i 2d much greater than t-(BuNPrEt)-Et-i 2e. The reactivity of the corresponding borane adducts toward 1-octene increases in the reverse order. The following amines form highly reactive liquid borane adducts hydroborating 1-octene in tetrahydrofuran at room temperature in less than 1 h: t-BuN(CH2CH2OMe)(2), t-(BuNBuEt)-Et-i, and t-(BuNPrMe)-Me-i. The limit of borane complexation among the amines examined is reached for t-BuNBu2i exchanging borane neither with EMS nor with BH3-THF. Among the various borane adducts prepared, the more promising borane adducts, t-Bu(CH3OCH2CH2)(2)N-BH3 (7), t-(BuMePrN)-N-i-BH3 (8), and t-(BuEtBuN)-N-i-BH3 (9), were selected for complete hydroboration and reduction studies. Hydroboration studies with the new, highly reactive trialkylamine-borane adducts 7-9 and representative olefins, such as l-hexene, styrene, beta-pinene, cyclopentene, norbornene, cyclohexene, 2-methyl-2-butene, alpha-pinene, and 2,3-dimethyl-2-butene, in tetrahydrofuran, dioxane, tert-butyl methyl ether, n-pentane, and dichloromethane, at room temperature (22 +/- 3 degrees C) were carried out. The reactions are faster in dioxane, requiring 1-2 h for the hydroboration of simple, unhindered olefins to the trialkylborane stage. Moderately hindered olefins, such as cyclohexene and 2-methyl-2-butene, give the corresponding dialkylboranes rapidly, with further slow hydroboration. However, the more hindered olefins, alpha-pinene and 2,3-dimethyl-2-butene, give stable monoalkylboranes very rapidly, with further hydroboration proceeding relatively slowly. The hydroborations can also be carried out conveniently in other solvents, such as THF, tert-butyl methyl ether, and n-pentane. A significant; rate retardation is observed in dichloromethane. Regioselectivity studies of l-hexene and styrene using these amine-borane adducts show selectivities similar to that of BH3-THF. The rates and stoichiometry of the reaction of t-BuMePriN-BH3 in tetrahydrofuran with selected organic compounds containing representative functional groups were also examined at room temperature. The reductions of esters, amides, and nitriles, which exhibit a sluggish reaction at room temperature, proceed readily under reflux conditions in tetrahydrofuran and dioxane and without solvent (at 85-90 degrees C). The carrier amines can be recovered by simple acid-base manipulations in good yield and readily recycled to make the borane adducts.
• Brown, H. C.; Klender, G. J., Inorganic Chemistry, 1962, vol. 1, p. 204 - 214
  作者：Brown, H. C.、Klender, G. J.

  DOI：——

  日期：——
• Gmelin Handbuch der Anorganischen Chemie, Gmelin Handbook: B: B-Verb.14, 4.4.2.4.1, page 189 - 191
  作者：

  DOI：——

  日期：——