环己酮三甲氧基甲硅烷基烯醇醚 | 332041-60-8

• 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
• 中文名称: 环己酮三甲氧基甲硅烷基烯醇醚
• 英文名称: (1-cyclohexenyloxy)trimethoxysilane
• 英文别名: Cyclohexanone trimethoxysilyl enol ether；1-trimethoxysilyloxycyclohexene；Silicic acid (H4SiO4), 1-cyclohexen-1-yl trimethyl ester；cyclohexen-1-yl trimethyl silicate
• CAS: 332041-60-8
• 化学式: C₉H₁₈O₄Si
• 分子量: 218.325
• InChiKey: QXTMYRKNZHTGRZ-UHFFFAOYSA-N

物化性质

• 沸点：
  235.3±10.0 °C(Predicted)
• 密度：
  1.02±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.84
• 重原子数：
  14
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  36.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  对溴苯甲醛 、 环己酮三甲氧基甲硅烷基烯醇醚 在 (R)-p-Tol-BINAP*AgF 作用下， 以 甲醇 为溶剂， 反应 4.0h， 以87%的产率得到2-(hydroxy-(4-bromophenyl)methyl)cyclohexan-1-one
  参考文献：
  名称：

  p-Tol-BINAP·AgF配合物催化三甲氧基甲硅烷基烯醇醚与醛的对映选择性羟醛反应

  摘要：

  以对 Tol-BINAP - AgF 复合物为催化剂，利用三甲氧基硅基烯醇醚实现了新的催化不对称 Mukaiyama 型醛醇反应。E 型和 Z 型硅烷烯醇醚均获得了较高的合成和对映体选择性。

  DOI：

  10.1055/s-2001-9715
• 作为产物：
  描述：

  2-环己烯-1-酮 、 三甲氧基硅烷 在 Wilkinson's catalyst 作用下， 生成 环己酮三甲氧基甲硅烷基烯醇醚
  参考文献：
  名称：

  p-Tol-BINAP·AgF配合物催化三甲氧基甲硅烷基烯醇醚与醛的对映选择性羟醛反应

  摘要：

  以对 Tol-BINAP - AgF 复合物为催化剂，利用三甲氧基硅基烯醇醚实现了新的催化不对称 Mukaiyama 型醛醇反应。E 型和 Z 型硅烷烯醇醚均获得了较高的合成和对映体选择性。

  DOI：

  10.1055/s-2001-9715

文献信息

• BINAP/AgOTf/KF/18-Crown-6 as New Bifunctional Catalysts for Asymmetric Sakurai−Hosomi Allylation and Mukaiyama Aldol Reaction
  作者：Manabu Wadamoto、Nobuko Ozasa、Akira Yanagisawa、Hisashi Yamamoto

  DOI：10.1021/jo020691c

  日期：2003.7.1

  A catalytic amount of KF.18-crown-6 complex is effective as a soluble fluoride source to activate an asymmetric Sakurai-Hosomi allylation with BINAP and silver(I) triflate catalyst. The allylation of a variety of aromatic, alpha,beta-unsaturated and aliphatic aldehydes with allylic trimethoxysilane resulted in high yields and remarkable enantioselectivities. In addition, the asymmetric Mukaiyama-type

  催化量的KF.18-crown-6配合物可有效用作可溶氟化物源，以活化BINAP和三氟甲磺酸银（I）催化的不对称Sakurai-Hosomi烯丙基化反应。多种芳族，α，β-不饱和和脂肪族醛与烯丙基三甲氧基硅烷的烯丙基化可实现高收率和显着的对映选择性。另外，通过在相同催化剂的存在下使用三甲氧基甲硅烷基烯醇醚来实现不对称的Mukaiyama型醛醇缩合反应。从E-甲硅烷基烯醇醚获得高的抗选择性，而Z-甲硅烷基烯醇醚产生顺选择性。
• Chiral base-catalyzed aldol reaction of trimethoxysilyl enol ethers: effect of water as an additive on stereoselectivities
  作者：Yuya Orito、Shunichi Hashimoto、Tadao Ishizuka、Makoto Nakajima

  DOI：10.1016/j.tet.2005.09.074

  日期：2006.1

  An aldol reaction of trimethoxysilyl enol ether catalyzed by lithium binaphtholate is described. The aldol reaction of trimethoxysilyl enol ether derived from cyclohexanone under anhydrous conditions predominantly afforded the anti-aldol adduct with moderate enantioselectivity, whereas the reaction under aqueous conditions predominantly resulted in the syn-adduct and the enantioselectivity of the syn-adduct

  描述了由双邻苯二甲酸锂催化的三甲氧基甲硅烷基烯醇醚的醛醇缩合反应。从环己酮衍生的无水条件下的三甲氧基甲硅烷烯醇醚醛醇缩合反应，得到主要的抗中度对映选择性加成物-aldol，而在含水条件下反应主要导致顺-adduct和的对映选择性合成-adduct被显着提高。在源自1-茚满酮的三甲氧基甲硅烷基烯醇醚与环己烷甲醛（97％ee（syn））的反应中获得最佳对映选择性。这是手性碱催化的三甲氧基甲硅烷基烯醇醚的醛醇缩合反应的第一个例子。
• Catalytic Asymmetric Aldol Reaction of Trimethoxysilyl Enol Ethers Using 2,2′-Bis(di-<i>p</i>-tolylphosphino)-1,1′-binaphthyl·AgF Complex
  作者：Akira Yanagisawa、Yoshinari Nakatsuka、Kenichi Asakawa、Manabu Wadamoto、Hiromi Kageyama、Hisashi Yamamoto

  DOI：10.1246/bcsj.74.1477

  日期：2001.8

  Catalytic asymmetric Mukaiyama-type aldol reaction using trimethoxysilyl enol ethers was achieved using 2,2′-bis(di-p-tolylphosphino)-1,1′-binaphthyl (p-Tol-BINAP)·AgF complex as a catalyst. The chiral silver(I) catalyst was easily generated by mixing p-Tol-BINAP and silver(I) fluoride in MeOH at room temperature. High syn- and enantioselectivities were obtained from both the E- and Z-silyl enol ethers

  以2,2'-双(二-对甲苯基膦基)-1,1'-联萘(p-Tol-BINAP)·AgF配合物为催化剂，实现了三甲氧基甲硅烷基烯醇醚催化不对称Mukaiyama型羟醛反应。通过在室温下将 p-Tol-BINAP 和氟化银 (I) 在 MeOH 中混合，很容易生成手性银 (I) 催化剂。E-和Z-甲硅烷基烯醇醚都获得了高的顺对映选择性。在环己酮衍生的三甲氧基甲硅烷基烯醇醚的反应中使用 MeOH 和丙酮的 1:1 混合物作为溶剂导致更高的对映选择性。
• Construction of quaternary carbon centers by a base-catalyzed enantioselective aldol reaction and related reactions of trimethoxysilyl enol ethers
  作者：Tomonori Ichibakase、Tetsuya Kaneko、Yuya Orito、Shunsuke Kotani、Makoto Nakajima

  DOI：10.1016/j.tet.2012.03.096

  日期：2012.6

  The aldol reactions of trimethoxysilyl enol ethers catalyzed by lithium binaphtholate were found to be powerful tools for the construction of quaternary asymmetric carbon centers. The stereoselectivities were greatly affected by the presence of water. Trimethoxysilyl enol ether derived from a cyclic ketone, such as cyclohexanone, was used as a substrate to obtain the anti-adduct preferentially under anhydrous conditions; by contrast, the syn-adduct was preferentially obtained under aqueous conditions with high stereoselectivity. The aldol-Tishchenko reaction of a trimethoxysilyl enol ether derived from acyclic ketones proceeded to give monoacyl 1,3-diol derivatives in high enantioselectivities. (C) 2012 Elsevier Ltd. All rights reserved.
• Enantioselective Aldol Reaction of Trimethoxysilyl Enol Ether Catalyzed by Lithium Binaphtholate
  作者：Makoto Nakajima、Yuya Orito、Tadao Ishizuka、Shunichi Hashimoto

  DOI：10.1021/ol048485+

  日期：2004.10.1

  (GRAPHICS)An aldol reaction of trimethoxysilyl enol ether catalyzed by lithium binaphtholate, in which water serves as an additive and plays a pivotal role in stereoselectivitles, was developed. This is the first example of an aldol reaction of trimethoxysilyl enol ether catalyzed by a chiral base.