(Z)-β(tert.-Butyldimethylsilyloxy)-β-methoxystyrol | 58367-63-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (Z)-β(tert.-Butyldimethylsilyloxy)-β-methoxystyrol
• 英文别名: tert-butyl-[(Z)-1-methoxy-2-phenylethenoxy]-dimethylsilane
• CAS: 58367-63-8
• 化学式: C₁₅H₂₄O₂Si
• 分子量: 264.44
• InChiKey: WCAMFRFLPQLMMK-OWBHPGMISA-N

物化性质

• 沸点：
  298.0±33.0 °C(Predicted)
• 密度：
  0.952±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.65
• 重原子数：
  18
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (Z)-β(tert.-Butyldimethylsilyloxy)-β-methoxystyrol 在 盐酸 、 N-甲基吲哚酮 、 Jacobsen's catalyst 、 4-MeO-PBA 作用下， 生成 DL-扁桃酸甲酯
  参考文献：
  名称：

  通过（salen）Mn（III）催化的甲硅烷基烯醇醚和甲硅烷基乙烯酮缩醛的氧化合成旋光性α-羟基羰基化合物

  摘要：

  光学活性的α-羟基酮和酯是通过（salen）Mn（III）催化的高对映选择性的甲硅烷基烯醇醚和甲硅烷基烯酮缩醛的不对称氧化反应制备的，ee值高达81％。对α-羟基酯为57％。转化的程度和对映选择性在很大程度上取决于氧供体的类型，水性漂白剂介质的pH值，添加剂以及烯醇官能度的取代方式。

  DOI：

  10.1016/0040-4039(96)01441-4
• 作为产物：
  描述：

  叔丁基二甲基氯硅烷 、 苯乙酸甲酯 生成 (Z)-β(tert.-Butyldimethylsilyloxy)-β-methoxystyrol
  参考文献：
  名称：

  The ester enolate Claisen rearrangement. Stereochemical control through stereoselective enolate formation

  摘要：

  DOI：

  10.1021/ja00426a033

文献信息

• Synthesis of Optically Active α-Hydroxy Carbonyl Compounds by the Catalytic, Enantioselective Oxidation of Silyl Enol Ethers and Ketene Acetals with (Salen)manganese(III) Complexes
  作者：Waldemar Adam、Rainer T. Fell、Veit R. Stegmann、Chantu R. Saha-Möller

  DOI：10.1021/ja9726668

  日期：1998.2.1

  A set of silyl enol ethers and ketene acetals 1a−h with α- and/or β-phenyl as well as alkyl substituents of different steric bulk has been submitted to the enantioselective catalytic oxidation by chiral (salen)MnIII complexes 3. Highest conversions and best enantioselectivities have been obtained with bleach rather than iodosobenzene as oxygen source for the active oxo−metal species. With regard to

  一组具有 α- 和/或 β-苯基以及不同空间体积的烷基取代基的甲硅烷基烯醇醚和烯酮缩醛 1a-h 已通过手性 (salen) MnIII 配合物进行对映选择性催化氧化 3. 最高转化率和使用漂白剂而不是碘苯作为活性氧金属物种的氧源获得了最佳的对映选择性。关于底物结构，对于在甲硅烷氧​​基位置具有短且未支化的烷基取代基的烯醇醚，ee 值已达到高达 89%。虽然 β-苯基有利于对映面控制，但在甲硅烷氧​​基官能团的 α 苯基取代基会导致较低的 ee 值，而二苯基取代的衍生物 1d 显示出最低的立体选择性。
• Copper-Catalyzed Amination of Silyl Ketene Acetals with <i>N</i>-Chloroamines
  作者：Tomoya Miura、Masao Morimoto、Masahiro Murakami

  DOI：10.1021/ol302331k

  日期：2012.10.19

  A copper(I)/2,2′-bipyridyl complex catalyzes an amination reaction of silyl ketene acetals with N-chloroamines, presenting a new preparative method of α-amino esters.

  铜（I）/ 2,2'-联吡啶配合物催化甲硅烷基乙烯酮缩醛与N-氯胺的胺化反应，为α-氨基酯的制备提供了一种新的方法。
• Stereochemistry of Silyl Ketene Acetals of Some 8-Phenylmenthyl Arylacetates
  作者：Arlette Solladie-Cavallo、Aurelio G. Csaky

  DOI：10.1021/jo00088a048

  日期：1994.5

  Trimethylsilyl ketene acetals derived from 8-phenylmenthyl phenyl-, p-fluorophenyl, and p-(trifluoromethyl)phenylacetates, methyl phenylacetate, and isopropyl phenylacetate have been studied. It was shown that it is not possible, under kinetic conditions, to form exclusively the desired E-isomer and that the thermodynamic Z-isomer is also obtained as the major product under reaction conditions which can be considered kinetic. The results could be rationalized using the Ireland's and Dauben's models on the basis of the changes in the acidity of the proton to be abstracted and the strength of the base. Dimethyl-tert-butylsilyl ketene acetals have also been studied. It appeared that reaction of TBDMSCl onto the Li-enolates favored the E-isomer. We proposed that, at the temperature (above -20 degrees C) at which the reaction occurs, the E-Z equilibrium between the Li-enolates starts to play a role, and therefore the silyl ketene acetals E/Z ratios are kinetically controlled but by the second step (reaction of the reagent onto the Li-enolate).
• Regiospecific ortho oxyfunctionalization of substituted benzenes with singlet oxygen
  作者：Isao Saito、Ryu Nagata、Hiyoshizo Kotsuki、Teruo Matsuura

  DOI：10.1016/s0040-4039(00)87198-1

  日期：1982.1
• Organolanthanide catalysis of a Mukaiyama addition reaction
  作者：Leyi Gong、Andrew Streitwieser

  DOI：10.1021/jo00313a002

  日期：1990.12

  Bis[bis(1,3-trimethylsilyl)cyclopentadienyl]-ytterbium(III) chloride, Cp''2YbCl, 2, is an effective catalyst in the presence of additional trimethylsilyl chloride for the reaction of silyl ester enolates, such as the trimethylsilyl enolate of methyl isobutyrate, 1, with aliphatic and aromatic aldehydes, to yield beta-silyloxy esters. The reaction shows good diastereoselection that is readily rationalized with a cyclic transition-state mechanism in which a key feature is the important role played by restricted coordination space around the lanthanide cation.