(E)-tert-Butylketene Methyl tert-Butyldimethylsilyl Acetal | 58367-56-9

• 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: (E)-tert-Butylketene Methyl tert-Butyldimethylsilyl Acetal
• 英文别名: (E)-[(1-tert-butoxy)propenyloxy]-tert-butyldimethylsilane；(E)-1-(tert-Butyldimethylsilyloxy)-1-methoxy-3,3-dimethyl-1-buten；tert-butyl-[(E)-1-methoxy-3,3-dimethylbut-1-enoxy]-dimethylsilane
• CAS: 58367-56-9
• 化学式: C₁₃H₂₈O₂Si
• 分子量: 244.45
• InChiKey: MVYXMFAKFZXJQL-ZHACJKMWSA-N

物化性质

• 沸点：
  244.6±23.0 °C(Predicted)
• 密度：
  0.857±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.54
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.85
• 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：

  (E)-tert-Butylketene Methyl tert-Butyldimethylsilyl Acetal 在 溶剂黄146 作用下， 以 氘代氯仿 为溶剂， 反应 0.08h， 以100%的产率得到叔丁乙酸甲酯
  参考文献：
  名称：

  E/Z isomerization, solvolysis, addition, and cycloaddition reactions of (E)-tert-butylketene methyl tert-butyldimethylsilyl acetal

  摘要：

  In the presence of catalytic amounts of CF3COCH3 or CF3COCF3, the silyl ketene acetal E-1 was isomerized into its Z isomer (Z/E ratio 90:10). For this novel E/Z isomerization a mechanism is proposed, in which addition and reelimination of the fluoro ketone, through a 1,4-dipolar intermediate operates. With the protic nucleophiles CH3OH, CF3CH2OH, or PhOH, the ketene acetal E-1 afforded the ortho esters 2 as addition products, while CH3CO2H, CF3CO2H, or H2O led to methyl pivalate as the solvolysis product. This chemistry is readily explained through protonation of the ketene acetal E-1 to generate the corresponding carbenium ion. At low temperature the reaction with TCNE gave the silylketene imine 3 as labile cycloadduct, which underwent on workup desilylation to give the TCNE-incorporated ester 6; the latter eliminated hydrogen cyanide at room temperature to give the ene ester 7. With MTAD the labile silyl ene product 4 was obtained initially, which underwent silyl migration to give N-silylated urazole 8; final desilylation led to the stable urazole 9. Also for the ene reactions of TCNE and MTAD with the silyl ketene acetal E-1, a 1,4-dipolar intermediate is proposed to intervene.

  DOI：

  10.1021/jo00026a013
• 作为产物：
  描述：

  叔丁乙酸甲酯 、 叔丁基二甲基氯硅烷 在 六甲基磷酰三胺 、 正丁基锂 、 异丙胺 作用下， 生成 (E)-tert-Butylketene Methyl tert-Butyldimethylsilyl Acetal
  参考文献：
  名称：

  Photooxygenation of silyl ketene acetals: dioxetanes as precursors to .alpha.-silylperoxy esters in the silatropic ene reaction

  摘要：

  Photooxygenation of silyl ketene acetals afforded dioxetanes, which subsequently underwent secondary reactions to give rearrangement products (alpha-silylperoxy esters, major products) and cleavage products (pivalaldehyde, minor product). The kinetics of these reactions were studied by NMR and chemiluminescence. The activation energy of the chemiluminescent cleavage process was 2-3 kcal/mol higher than that of the rearrangement. In the presence of catalytic amounts of CF3COCF3 or CF3COCH3, the (E)-silyl ketene acetals rearranged into their Z isomers. Photooxygenation of the (E)- and (Z)-silyl ketene acetals showed that the [2 + 2] cycloaddition was rigorously diastereoselective. Trapping experiments with acetaldehyde confirmed the intermediacy of 1,4-zwitterions in the rearrangement of the (E)- and (Z)-dioxetanes into alpha-silylperoxy esters, but such intermediates were not detected during the photooxygenation of the silyl ketene acetals; the latter proceeds presumably via perepoxides.

  DOI：

  10.1021/jo00015a030

文献信息

• Lewis Base Activation of Lewis Acids. Addition of Silyl Ketene Acetals to Aldehydes
  作者：Scott E. Denmark、Thomas Wynn、Gregory L. Beutner

  DOI：10.1021/ja0282947

  日期：2002.11.1

  olefinic aldehydes as well as aliphatic aldehydes (albeit more slowly) with excellent enantioselectivity. The homologous tert-butyldimethylsilyl ketene acetal of tert-butyl propanoate adds with nearly exclusive anti diastereoselectivity to a similar range of aldehydes also with excellent enantioselectivity. The origin of the slower reaction rate with aliphatic aldehydes is revealed to be the formation of chlorosilyl

  弱路易斯酸四氯化硅可以被催化量的手性双磷酰胺 (R,R)-3 活化，形成高反应性的手性三氯甲硅烷基阳离子，它是醛和甲硅烷基乙烯酮缩醛之间羟醛加成反应的极其有效的促进剂。乙酸甲酯的叔丁基二甲基甲硅烷基乙烯酮缩醛几乎立即添加到芳香族和烯烃醛以及脂肪族醛中（尽管速度更慢），具有出色的对映选择性。丙酸叔丁酯的同源叔丁基二甲基甲硅烷基乙烯酮缩醛为类似范围的醛类添加了几乎独有的抗非对映选择性，同时也具有出色的对映选择性。与脂肪醛反应速度较慢的原因是氯甲硅烷基醚加合物的形成。
• The ester enolate Claisen rearrangement. Stereochemical control through stereoselective enolate formation
  作者：Robert E. Ireland、Richard H. Mueller、Alvin K. Willard

  DOI：10.1021/ja00426a033

  日期：1976.5
• Dimethyldioxirane epoxidation of alkenes bearing two electron donating substituents.
  作者：Waldemar Adam、Lazaros Hadjarapoglou、Xiaoheng Wang

  DOI：10.1016/s0040-4039(00)79649-3

  日期：1991.3

  Various enol-type alkenes, such as 2,3-dimethylbenzodioxin (1), O-tetrabenzyl glycal (3), 1,2-bis(trimethylsilyloxy)cycloalkenes (9) were transformed in excellent yields to their labile epoxides by dimethyldioxirane (as acetone solution); the silyl ketene acetal 5 and 2-methyl-3-trimethylsilyloxybenzo[b]furan (7) gave the corresponding epoxide rearrangement products.