5-(9-Borabicyclo[3.3.1]nonan-9-yl)pentoxy-tri(propan-2-yl)silane | 1258222-46-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 金属杂环化合物
• 英文名称: 5-(9-Borabicyclo[3.3.1]nonan-9-yl)pentoxy-tri(propan-2-yl)silane
• 英文别名: 5-(9-borabicyclo[3.3.1]nonan-9-yl)pentoxy-tri(propan-2-yl)silane
• CAS: 1258222-46-6
• 化学式: C₂₂H₄₅BOSi
• 分子量: 364.495
• InChiKey: GILZRRKFHVSABR-UHFFFAOYSA-N

物化性质

• 沸点：
  413.1±24.0 °C(predicted)
• 密度：
  0.87±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  7.95
• 重原子数：
  25
• 可旋转键数：
  10
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  5-(9-Borabicyclo[3.3.1]nonan-9-yl)pentoxy-tri(propan-2-yl)silane 在 1,10-菲罗啉 、 potassium tert-butylate 、 copper (I) acetate 作用下， 以 甲醇 、 乙醚 、 甲苯 为溶剂， 100.0 ℃ 、101.33 kPa 条件下， 反应 12.0h， 生成 methyl 6-(triisopropylsilyloxy)hexanoate
  参考文献：
  名称：

  Copper-Catalyzed Carboxylation of Alkylboranes with Carbon Dioxide: Formal Reductive Carboxylation of Terminal Alkenes

  摘要：

  Carboxylation of alkylboron compounds (alkyl-9-BBN) with CO2 proceeded in the presence of catalytic amounts of CuOAc/1,10-phenanthroline and a stoichiometric amount of (KOBu)-Bu-t. The alkylboranes are easily and widely available through the alkene hydroboration, and thus the overall process represents a reductive carboxylation of alkenes with CO2. The broad functional group compatibility and the inexpensiveness of the Cu/1,10-phenathoroline catalyst system are attractive features of this protocol.

  DOI：

  10.1021/ol103128x
• 作为产物：
  描述：

  9-硼双环[3.3.1]壬烷 、 triisopropyl(pent-4-en-1-yloxy)silane 以 四氢呋喃 为溶剂， 反应 1.0h， 生成 5-(9-Borabicyclo[3.3.1]nonan-9-yl)pentoxy-tri(propan-2-yl)silane
  参考文献：
  名称：

  炔丙基磷酸酯与炔烃之间铜催化的γ-选择性和立体特异性偶联作用的Allene方法

  摘要：

  炔丙基磷酸酯和烷基硼化合物（烷基-9-BBN，通过烯烃与9-BBN-H的氢硼化反应制得）之间的铜催化γ-选择性偶合提供了具有各种官能团的多取代的烯。富含对映体的炔丙基磷酸酯生成轴向手性烯基的反应进行时，具有出色的点对轴手性转移，且具有1,3-抗立体化学。

  DOI：

  10.1021/ol202866h

文献信息

• Synthesis of Trisubstituted Alkenylstannanes through Copper-Catalyzed Three-Component Coupling of Alkylboranes, Alkynoates, and Tributyltin Methoxide
  作者：Takamichi Wakamatsu、Kazunori Nagao、Hirohisa Ohmiya、Masaya Sawamura

  DOI：10.1002/anie.201305973

  日期：2013.10.25

  A versatile route to trisubstituted alkenylstannanes is presented. The alkyl and Sn moieties were introduced at the β and α carbon atoms of alkynoates, respectively, in a formal syn addition mode with complete regioselectivity (see scheme). A variety of functional groups were tolerated in the alkylboranes and alkynoates.

  提出了一种通用的途径来制备三取代的链烯基锡烷。烷基和Sn部分分别以正式的顺式 加成模式和完全的区域选择性引入炔烃的β和α碳原子上（参见方案）。烷基硼烷和炔酸酯中可耐受多种官能团。
• Copper-Catalyzed Enantioselective Allylic Substitution with Alkylboranes
  作者：Yoshinori Shido、Mika Yoshida、Masahito Tanabe、Hirohisa Ohmiya、Masaya Sawamura

  DOI：10.1021/ja3093955

  日期：2012.11.14

  The first catalytic enantioselective allylic substitution reaction with alkylboron compounds has been achieved. The reaction between alkyl-9-BBN reagents and primary allylic chlorides proceeded with excellent γ-selectivities and high enantioselectivities under catalysis of a Cu(I)-DTBM-SEGPHOS system. The protocol produces terminal alkenes with an allylic stereogenic center branched with functionalized

  已经实现了与烷基硼化合物的第一个催化对映选择性烯丙基取代反应。在Cu(I)-DTBM-SEGPHOS体系的催化下，烷基-9-BBN试剂与伯烯丙基氯之间的反应具有优异的γ-选择性和高对映选择性。该协议产生具有烯丙基立体中心的末端烯烃，该中心带有功能化的 sp(3)-烷基基团。与γ-硅取代的烯丙基氯的反应为功能化的α-立体异构手性烯丙基硅烷的对映选择性合成提供了一种有效的策略。
• Construction of Quaternary Stereogenic Carbon Centers through Copper-Catalyzed Enantioselective Allylic Cross-Coupling with Alkylboranes
  作者：Kentaro Hojoh、Yoshinori Shido、Hirohisa Ohmiya、Masaya Sawamura

  DOI：10.1002/anie.201402386

  日期：2014.5.5

  primary allyl chlorides with enantiocontrol at a useful level. The reaction generates a stereogenic quaternary carbon center having three sp3‐alkyl groups and a vinyl group. This protocol allowed the use of terminal alkenes as nucleophile precursors, thus representing a formal reductive allylic cross‐coupling of terminal alkenes. A reaction pathway involving addition/elimination of a neutral alkylcopper(I)

  原位生成的手性Cu I / DTBM-MeO-BIPHEP催化剂系统与EtOK的结合使烷基硼烷试剂与γ，γ-二取代的伯烯丙基氯之间的对映选择性S N 2'型烯丙基交叉偶联以及对映体控制有效等级。该反应产生具有三个sp 3-烷基和一个乙烯基的立体异构的季碳中心。该协议允许使用末端烯烃作为亲核试剂的前体，因此代表了末端烯烃的正式还原性烯丙基交叉偶联。提出了一种涉及用烯丙基氯底物添加/消除中性烷基铜（I）物质的反应途径。
• The Catalytic Addition of Alkyl Boranes to Alkynyl Esters Affording Single-Isomer Trisubstituted Olefins
  作者：William Ogilvie、Thivisha Rajagopal

  DOI：10.1055/s-0030-1259933

  日期：2011.5

  The generation of a series of trisubstituted olefins bearing alkyl substituents is described using a stereoselective and regio­selective addition to alkynyl esters. The method produces trisubstituted olefins as single isomers using a convenient and mild transformation in which alkyl boranes are cross-coupled with alkynyl esters and amides using palladium catalysis.

  描述了一种生成一系列具有烷基取代基的三取代烯烃的方法，该方法采用选择性立体和选择性区位的加成反应至炔基酯。这种方法通过方便温和的转化生成单一异构体的三取代烯烃，其中烷基硼烷与炔基酯和酰胺通过钯催化进行交叉偶联反应。
• Single isomer trisubstituted olefins bearing alkyl groups
  作者：Thivisha Rajagopal、Alison B. Flynn、William W. Ogilvie

  DOI：10.1016/j.tet.2010.09.002

  日期：2010.11

  E-beta-Chloro-alpha-iodo-alpha,beta-unsaturated esters were converted to single isomer trisubstituted olefins bearing alkyl substituents by using and alkyl-Suzuki cross coupling. The process was highly selective, and the products in all cases were isolated as single isomers. Mechanistic investigations indicated that this process transfers a hydrogen from water to the alpha-position of the substrate, and then an alkyl group is introduced to the beta-position of the intermediate template while replacing a chloride. (C) 2010 Elsevier Ltd. All rights reserved.