trans-6-(tert-Butyldiphenylsiloxy)-3-hexene | 229982-22-3

• 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: trans-6-(tert-Butyldiphenylsiloxy)-3-hexene
• 英文别名: tert-butyl-[(E)-hex-3-enoxy]-diphenylsilane
• CAS: 229982-22-3
• 化学式: C₂₂H₃₀OSi
• 分子量: 338.565
• InChiKey: YQGYLKSXDHFBJF-VOTSOKGWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.92
• 重原子数：
  24
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.36
• 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：

  trans-6-(tert-Butyldiphenylsiloxy)-3-hexene 在 (bicyclo[2.2.1]hepta-2,5-diene)-(2,4-pentanedionato)-rhodium 、 1-(2-二苯基庚基1萘酚)硫酸甲基酯 双联邻苯二酚硼酸酯 、 sodium hydroxide 、 双氧水 作用下， 以 四氢呋喃 为溶剂， 反应 24.0h， 以77%的产率得到(3R,4R)-1-(tert-butyldiphenylsilanyloxy)-hexane-3,4-diol
  参考文献：
  名称：

  Rh-Catalyzed Enantioselective Diboration of Simple Alkenes:  Reaction Development and Substrate Scope

  摘要：

  The rhodium-catalyzed reaction between bis(catecholato)diboron and simple alkenes results in the syn addition of the diboron across the alkene. The resulting 1,2-bis(boronate) is subsequently oxidized to provide the 1,2-diol. In the presence of enantiomerically enriched Quinap ligand, high enantioselection in the diboration can be achieved. The reaction is highly selective for trans- and trisubstituted alkenes and can be selective for some monosubstituted alkenes as well. The development of this reaction is described as is the substrate scope and experiments that are informative about the reaction mechanism and competing pathways.

  DOI：

  10.1021/jo051651m
• 作为产物：
  描述：

  在 diethylzinc 、 甲醇 作用下， 以 甲苯 为溶剂， 反应 0.33h， 生成 trans-6-(tert-Butyldiphenylsiloxy)-3-hexene
  参考文献：
  名称：

  Kerrigan, Michael H.; Jeon, Sang-Jin; Chen, Young K., Journal of the American Chemical Society, 2009, vol. 131, p. 8434 - 8445

  摘要：

  DOI：

文献信息

• Enantio- and Regioselective Intermolecular Benzylic and Allylic CH Bond Amination
  作者：Yota Nishioka、Tatsuya Uchida、Tsutomu Katsuki

  DOI：10.1002/anie.201208906

  日期：2013.2.4

  Smooth salen: Ru(CO)–salen complex 1 is an effective catalyst for asymmetric benzylic and allylic CH bond amination using 2‐(trimethylsilyl)ethanesulfonyl azide (SESN3) as the nitrene source. The reaction proceeded with high enantioselectivity and excellent regioselectivity. An ethyl group can be selectively aminated, even in the presence of an n‐propyl group. No migration or isomerization of the

  平滑萨伦：钌（CO）-salen络合物1是用于非对称苄基和烯丙基℃的有效催化剂使用2-（三甲硅烷基）乙磺酰基叠氮化物（SESN H键胺化3）作为氮宾源。反应以高对映选择性和优异的区域选择性进行。即使存在正丙基，乙基也可以被选择性胺化。没有观察到双键的迁移或异构化。
• Iridium(III)-Catalyzed Asymmetric Site-Selective Carbene C–H Insertion during Late-Stage Transformation
  作者：Yuki Yamakawa、Takashi Ikuta、Hiroki Hayashi、Keigo Hashimoto、Ryoma Fujii、Kyohei Kawashima、Seiji Mori、Tatsuya Uchida、Tsutomu Katsuki

  DOI：10.1021/acs.joc.2c00470

  日期：2022.5.20

  late-stage material transformation is limited. Here, we observed that the iridium–salen complex 6 exhibited efficient catalysis in asymmetric carbene C–H insertion reactions. Under optimized conditions, benzylic, allylic, and propargylic C–H bonds were converted to desired C–C bonds in an excellent stereoselective manner. Excellent regioselectivity was demonstrated in the reaction using not only simple substrate

  C-H 官能化最近受到了相当多的关注，因为后期转化过程中的 C-H 官能化是修饰生物活性化合物和产生新活性分子的强大而有用的工具。虽然卡宾转移反应可以以立体选择性的方式直接将 C-H 键转化为所需的 C-C 键，但其在后期材料转化中的应用受到限制。在这里，我们观察到铱-萨伦络合物6在不对称卡宾C-H插入反应中表现出有效的催化作用。在优化条件下，苄基、烯丙基和炔丙基 C-H 键以优异的立体选择性方式转化为所需的 C-C 键。该反应不仅使用简单的底物，而且还使用天然产物，具有多个反应位点，表现出优异的区域选择性。此外，基于机理研究，铱催化的独特 C-H 插入反应涉及决定速率的异步协同过程。
• Carbohydrate/DBU Cocatalyzed Alkene Diboration: Mechanistic Insight Provides Enhanced Catalytic Efficiency and Substrate Scope
  作者：Lu Yan、Yan Meng、Fredrik Haeffner、Robert M. Leon、Michael P. Crockett、James P. Morken

  DOI：10.1021/jacs.7b12316

  日期：2018.3.14

  A mechanistic investigation of the carbohydrate/DBU cocatalyzed enantioselective diboration of alkenes is presented. These studies provide an understanding of the origin of stereoselectivity and also reveal a strategy for enhancing reactivity and broadening the substrate scope.
• Han, Hyunsoo; Cho, Chang-Woo; Janda, Kim D., Chemistry - A European Journal, 1999, vol. 5, # 5, p. 1565 - 1569
  作者：Han, Hyunsoo、Cho, Chang-Woo、Janda, Kim D.

  DOI：——

  日期：——
• Rh-Catalyzed Enantioselective Diboration of Simple Alkenes:  Reaction Development and Substrate Scope
  作者：Stéphane Trudeau、Jeremy B. Morgan、Mohanish Shrestha、James P. Morken

  DOI：10.1021/jo051651m

  日期：2005.11.1

  The rhodium-catalyzed reaction between bis(catecholato)diboron and simple alkenes results in the syn addition of the diboron across the alkene. The resulting 1,2-bis(boronate) is subsequently oxidized to provide the 1,2-diol. In the presence of enantiomerically enriched Quinap ligand, high enantioselection in the diboration can be achieved. The reaction is highly selective for trans- and trisubstituted alkenes and can be selective for some monosubstituted alkenes as well. The development of this reaction is described as is the substrate scope and experiments that are informative about the reaction mechanism and competing pathways.