1-tert-butyldiphenylsiloxy-1-cyclohexene | 152718-41-7

• 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: 1-tert-butyldiphenylsiloxy-1-cyclohexene
• 英文别名: tert-butyl(cyclohex-1-en-1-yloxy)diphenylsilane；tert-butyl(cyclohexenyloxy)diphenylsilane；Tert-butyl-(cyclohexen-1-yloxy)-diphenylsilane
• CAS: 152718-41-7
• 化学式: C₂₂H₂₈OSi
• 分子量: 336.549
• InChiKey: ICRXCUALFPEBQW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.02
• 重原子数：
  24
• 可旋转键数：
  5
• 环数：
  3.0
• 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：

  1-tert-butyldiphenylsiloxy-1-cyclohexene 在 Shi's ketone 、 Oxone 、 四丁基硫酸氢铵 、 potassium carbonate 作用下， 以 二甲醇缩甲醛 、 乙腈 为溶剂， 反应 2.0h， 以77%的产率得到((1R,6R)-7-oxa-bicyclo[4.1.0]heptan-1-yloxy)(tert-butyl)diphenylsilane
  参考文献：
  名称：

  Lim, Sang Min; Hill, Nicholas; Myers, Andrew G., Journal of the American Chemical Society, 2009, vol. 131, p. 5763 - 5765

  摘要：

  DOI：
• 作为产物：
  描述：

  环己酮 在 双(三甲基硅烷基)氨基钾 作用下， 反应 2.5h， 生成 1-tert-butyldiphenylsiloxy-1-cyclohexene
  参考文献：
  名称：

  A base-promoted deprotection of 1,3-dioxolanes to ketones

  摘要：

  An effective deprotection methodology of dioxolanes was developed, affording moderate to excellent yield via a LIMP-promoted reaction in THF, which displays admirable chemoselectivity in the presence of dimethylketal, 1,3-dioxane, 1,3-dithiane, or other acid-sensitive protective groups. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2012.10.037

文献信息

• One-Pot Synthesis of Silylated Enol Triflates from Silyl Enol Ethers for Cyclohexynes and 1,2-Cyclohexadienes
  作者：Kazuki Inoue、Ryo Nakura、Kentaro Okano、Atsunori Mori

  DOI：10.1002/ejoc.201800353

  日期：2018.7.6

  Regiocontrolled synthesis of precursors for strained cyclohexynes and 1,2‐cyclohexadienes is described based on one‐pot rearrangement of a silyl group followed by the formation of enol triflates. The transient α‐silylated lithium enolate was smoothly isomerized in the presence of stoichiometric amount of water within one hour at room temperature to provide precursors for cyclohexyne.

  基于甲硅烷基的一锅重排，然后形成烯醇三氟甲磺酸，描述了用于应变环己炔和1,2-环己二烯的前体的区域控制合成。在室温下在一小时内，在化学计量的水存在下，将瞬态α-甲硅烷基化的烯酸锂平稳异构化，以提供环己炔的前体。
• Highly Enantioselective [3+2] Annulation of Cyclic Enol Silyl Ethers with Donor-Acceptor Cyclopropanes: Accessing<i>3a</i>-Hydroxy [<i>n</i>.3.0]Carbobicycles
  作者：Hao Xu、Jian-Ping Qu、Saihu Liao、Hu Xiong、Yong Tang

  DOI：10.1002/anie.201300032

  日期：2013.4.2

  bisoxazoline (BOX)/CuII catalyst. This reaction works well with cyclic enol silyl ethers of different sizes, and can be extended to dienol and benzene‐fused substrates, thus providing an effective and general access to a range of 3a‐hydroxy [n.3.0]carbobicycles which are found as a core structure in many natural products. TBDPS=tert‐butyldiphenylsilyl.

  新的保险丝：使用新的双恶唑啉（BOX）/ Cu II催化剂实现了标题反应。该反应适用于不同大小的环状烯醇甲硅烷基醚，并且可以扩展至二烯醇和苯稠合的底物，从而提供有效且普遍的接触范围为3a-羟基[ n。3.0]碳双环被发现是许多天然产物的核心结构。TBDPS =叔丁基二苯基甲硅烷基。
• Construction of Highly-Functionalized Cyclopentanes from Silyl Enol Ethers and Activated Cyclopropanes by [3+2] Cycloaddition Catalyzed by Triflic Imide
  作者：Kiyosei Takasu、Satoshi Nagao、Masataka Ihara

  DOI：10.1002/adsc.200600308

  日期：2006.11

  [3+2] Cycloadditions of silyl enol ethers with donor-acceptor (D-A) cyclopropanes, such as 2-alkoxycyclopropanecarboxylates and 2-(p-methoxyphenyl)cyclopropyl phenyl ketone, proceed in the presence of a catalytic amount of triflic imide (Tf2NH) to give functionalized cyclopentanes in high yield. The catalytic process allows promotion of the cycloaddition of substrates incorporating Lewis basic functions

  [3 + 2]甲硅烷基烯醇醚与供体-受体（DA）环丙烷（如2-烷氧基环丙烷羧酸酯和2-（对甲氧基苯基）环丙基苯基酮）的环加成反应在催化量的三氟甲基酰亚胺（Tf 2 NH）以高产率得到官能化的环戊烷。催化过程允许促进结合了路易斯基本功能的底物例如醚和氨基甲酸酯部分的环加成。此外，已经证明了α，β-不饱和羰基化合物，2-甲硅烷二烯和DA环丙烷的多组分[4 + 2]-[3 + 2]级联环加成反应以形成高度官能化的双环[4.3.0]壬烷。
• Eu(fod)3 and SnCl4-catalyzed heterocycloadditions of O-silyl enol ethers deriving from cyclic ketones
  作者：Gilles Dujardin、Arnaud Martel、Eric Brown

  DOI：10.1016/s0040-4039(98)01969-8

  日期：1998.11

  O-t-Butyldimethylsilyl enol ethers deriving from simple cyclic ketones acted as efficient dienophiles in the Lewis acid-catalyzed heterocycloadditions with methyl benzylidenepyruvate 1. Good selectivities were observed with cyclohexanone derivatives. Using Eu(fod)3, the dienophile 2b led to the expected endo adduct 3b (93–97%). When using SnCl4, the major product (89–95%) was found to be the “abnormal”

  OT丁基二甲硅烷基烯醇醚从充当与甲基benzylidenepyruvate路易斯酸催化heterocycloadditions高效亲双烯体的简单环酮衍生1。用环己酮衍生物观察到良好的选择性。使用Eu（fod）3，双亲物2b产生了预期的内加合物3b（93–97％）。当使用SnCl 4时，发现主要产物（89–95％）是带有反式环结的“异常”加合物5b。
• Computationally Guided Stereocontrol of the Combined CH Functionalization/Cope Rearrangement
  作者：Yajing Lian、Kenneth I. Hardcastle、Huw M. L. Davies

  DOI：10.1002/anie.201103568

  日期：2011.9.26

  Diastereoselectivity in control: The synthetic utility of the CH functionalization/Cope rearrangement reaction has been greatly expanded by the design of substrates that will react through a boat transition state instead of a chair transition state. The products are formed with the opposite diastereoselectivity as previously obtained (see scheme, ABSA= acetamidobenzenesulfonylazide).

  控制中的非对映选择性：通过底物的设计， CH官能化/Cope重排反应的合成效用得到了极大的扩展，底物将通过船过渡态而不是椅过渡态进行反应。形成的产物具有与之前获得的相反的非对映选择性（参见方案，ABSA=乙酰氨基苯磺酰叠氮）。