tris(2-methyl-2-propenyl)borane | 32784-73-9

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: tris(2-methyl-2-propenyl)borane
• 英文别名: trimethallylborane；Borane, tris(2-methyl-2-propenyl)-；tris(2-methylprop-2-enyl)borane
• CAS: 32784-73-9
• 化学式: C₁₂H₂₁B
• 分子量: 176.11
• InChiKey: QFLCKJNDYQEVBZ-UHFFFAOYSA-N

物化性质

• 沸点：
  219.8±39.0 °C(Predicted)
• 密度：
  0.755±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.21
• 重原子数：
  13
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  tris(2-methyl-2-propenyl)borane 生成 3-Methoxy-7-methylen-1,5-dimethyl-3-borabicyclo<3.3.1>nonan
  参考文献：
  名称：

  Boroorganic compounds

  摘要：

  DOI：

  10.1007/bf02659537
• 作为产物：
  描述：

  甲基烯丙基溴化镁 在 三氟化硼乙醚 作用下， 以 四氢呋喃 为溶剂， 反应 0.5h， 生成 tris(2-methyl-2-propenyl)borane
  参考文献：
  名称：

  使用烯丙基卤化物和烯丙基金属化合物烯丙基化醛二氨基巯基三嗪酮

  摘要：

  4-amino-3-mercapto-6-methyl-4H-1,2,4-triazin-5-one (1) 及其亚芳基氨基衍生物 5 的烯丙基化是通过两种不同的方法进行的。在乙醇钠存在下，1和5与烯丙基溴2的反应得到S-和N-烯丙基化产物的混合物。用烯丙基溴化锌 9 和三烯丙基硼烷试剂 12 处理芳基亚胺 5 不影响杂环开环，但侧链的 CN 键发生加成反应，产生 C-烯丙基化产物 10。 © 2003 Wiley Periodicals, Inc. Heteroatom Chem 14:280–287, 2003; 在线发表于 Wiley InterScience (www.interscience.wiley.com)。DOI 10.1002/hc.10144

  DOI：

  10.1002/hc.10144
• 作为试剂：
  描述：

  (2S,6R)-2,6-bis(2-methylprop-2-enyl)-1,2,5,6-tetrahydropyridine 在 镍 甲醇 、 sodium hydroxide 、 氢气 、 tris(2-methyl-2-propenyl)borane 作用下， 以 溶剂黄146 为溶剂， 反应 13.5h， 生成 cis-2,6-Diisobutylpiperidine
  参考文献：
  名称：

  Transformations of pyridine and deuteropyridine under the action of trimethallylborane and alcohols. Synthesis oftrans- andcis-2,6-dimethallyl-1,2,3,6-tetrahydropyridines and theirN-derivatives

  摘要：

  Reductive trans-2,6-dimethallylation of pyridine and deuteropyridine with trimethallylborane in the presence of alcohols proceeds at room temperature, i.e., under substantially milder conditions than the analogous reaction with the participation of triallylborane. trans-2,6-Di(2-methylallyl)-1 ,2,3,6-tetrahydropyridine (3) was obtained in a yield of 87%. When heated with trimethallylborane (130-135 degrees C, 2.5 h), compound 3 underwent isomerization to cis-2,6-di(2-methylallyl)-1,2,3,6-tetrahydropyridine (4). Hydrogenation of trans-(3) and cis-isomers (4) yielded trans-and cis-2,6-diisobutylpiperidines, respectively. The heterocycles obtained were N-functionalized by reactions with Mel, PhCH2Cl, ethylene oxide, and perfluoropropyloxirane. The stereochemistry of the cis-and trans-isomers (3 and 4) was established based on the NMR spectra of their N,N-dimethyl salts and the products of the reaction with ethylene oxide. trans-2,6-Dimethallyl-2,3,4,5,6-pentadeutero,2,3, 6-tetrahydropyridine and a number of its derivatives were prepared from the complex of trimethallylborane with C5D5N A probable mechanism of the reductive trans-2,6-diallylation of pyridines with allylboranes in the presence of alcohols is discussed.

  DOI：

  10.1007/bf02495933

文献信息

• Enantioselective Synthesis of Cyclic Amides and Amines through Mo-Catalyzed Asymmetric Ring-Closing Metathesis
  作者：Elizabeth S. Sattely、G. Alexander Cortez、David C. Moebius、Richard R. Schrock、Amir H. Hoveyda

  DOI：10.1021/ja051330s

  日期：2005.6.1

  investigations, a catalytic asymmetric method for highly enantioselective (up to 97% ee) synthesis of small- and medium-ring unsaturated cyclic amines is reported; optically enriched products bear a secondary amine or a readily removable Cbz or acetamide unit. Regio- and diastereoselective functionalizations of olefins within the optically enriched amine products have been carried out. Both catalytic asymmetric

  首先，报道了一种合成光学富集的 N 稠合双环结构的有效方法。通过 Mo 催化的非手性多烯底物的去对称化，可以合成 5,6-、5,7- 和 5,8- 双环酰胺，ee 高达 >98%。详细检查和讨论了催化剂结构、烯烃取代、路易斯碱性官能团的定位和环尺寸的影响。在研究的第二阶段，报道了一种用于高度对映选择性（高达 97% ee）合成中小环不饱和环胺的催化不对称方法；光学富集的产品带有仲胺或易于去除的 Cbz 或乙酰胺单元。已经在光学富集的胺产品中进行了烯烃的区域选择性和非对映选择性官能化。两种催化不对称方法都包括导致形成三取代和二取代环状烯烃的转化。本文概述的方案提供了各种高光学纯度的环胺；此类产品不易通过替代方案获得，可用于生物活性分子的对映选择性全合成。
• Enantioselective allylation of N-(trimethylsilyl)benzaldehyde imine using polymer-supported chiral allylboron reagents
  作者：Ashraf A El-Shehawy、Magdy Y Abdelaal、Katsuhiro Watanabe、Koichi Ito、Shinichi Itsuno

  DOI：10.1016/s0957-4166(97)00184-5

  日期：1997.6

  trimethallylborane, and tri(3,3-dimethylallyl)borane, respectively, to give polymeric allylating agents. N-(Trimethylsilyl)benzaldehyde imine was allowed to react with the polymeric chiral reagents to afford the corresponding primary homoallylamines in high yield and good enantioselectivities.

  将由（1 R）-（+）樟脑的对映体纯氨基醇1c和2c与苯乙烯和二乙烯基苯共聚获得的聚合物负载的手性N-磺酰基氨基醇3和4用三烯丙基硼烷，三甲基烯丙基硼烷和三（3， 3-二甲基烯丙基）硼烷分别得到聚合的烯丙基化剂。使N-（三甲基甲硅烷基）苯甲醛亚胺与聚合物手性试剂反应，以高收率和良好的对映选择性提供相应的伯均烯丙基胺。
• Organoboron compounds. Allylboration of carbonyl compounds with allyl(alkyl)boranes
  作者：B.M. Mikhailov、Yu.N. Bubnov、A.V. Tsyban'、M.Sh. Grigoryan

  DOI：10.1016/s0022-328x(00)83434-8

  日期：1978.1

  convenient procedure for the synthesis of homoallylic alcohols from carbonyl compounds and allylboranes is described. Allyl-, 2-methylallyl-, crotyl- and 3,3-dimethylallyl(dialkyl)boranes, as well as diallyl(alkyl)boranes and derivatives of 3-allyl- and 3-metallyl-3-borabicyclo[3.3.1]non-6-ene are effective reagents for allylation of carbonyl compounds (aldehydes, ketones, esters, carboxylic acids and others)

  描述了一种从羰基化合物和烯丙基硼烷合成均烯丙基醇的简便方法。烯丙基，2-甲基烯丙基，巴豆基和3,3-二甲基烯丙基（二烷基）硼烷，以及二烯丙基（烷基）硼烷和3-烯丙基和3-金属烯丙基-3-borabicyclo [3.3.1] non的衍生物-6-烯是用于羰基化合物（醛，酮，酯，羧酸等）的烯丙基化的有效试剂，在许多情况下，与使用相应的烯丙基卤化镁相比，具有相当大的优势。羰基化合物的烯丙基硼化与烯丙基重排有关。同时将巴豆基和3,3-二甲基-烯丙烯酮反应成具有末端双键的均烯丙基醇。
• A Convenient Synthesis of 2,2-Diallylated Nitrogen Heterocycles by Allylboration of Lactams
  作者：Yuri N. Bubnov、Fedor V. Pastukhov、Ilia V. Yampolsky、Anatoli V. Ignatenko

  DOI：10.1002/(sici)1099-0690(200004)2000:8<1503::aid-ejoc1503>3.0.co;2-7

  日期：2000.4

  Lactams containing an N-H bond are smoothly transformed into 2,2-diallylated nitrogen heterocycles on heating with allylic boranes in THF followed by deboronation

  在THF中与烯丙基硼烷一起加热，然后将含NH键的内酰胺平滑转化为2，2-二烯丙基化的氮杂环
• Preparation of Both Diastereomers of Homoallylic Amines by Allylmetalation of Methyl <i>N</i>-Benzylidene-(<i>S</i>)-valinate
  作者：Ashraf A. El-Shehawy、Mahmoud A. Omara、Koichi Ito、Shinichi Itsuno

  DOI：10.1055/s-1998-1681

  日期：1998.4

  The reaction of enantiopure imine 1 with methallyl or prenylzinc reagents affords homoallylic amines having (S,S) configuration with up to 100% diastereomeric excess. Another diastereomer, (R,S)-amines, is obtained from the same imine 1 by using allylboron reagents.

  手性纯烯胺1与甲基丙烯基或普伦基锌试剂的反应生成具有(S,S)构型的同伴胺，反应的二级立体化合物过量可达100%。另一种二级立体异构体(R,S)-胺则是通过使用烯基硼试剂从同一烯胺1获得的。