(E)-6-(tert-Butyl-dimethyl-silanyloxy)-2-methyl-hex-2-enal | 933456-60-1

• 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)-6-(tert-Butyl-dimethyl-silanyloxy)-2-methyl-hex-2-enal
• CAS: 933456-60-1
• 化学式: C₁₃H₂₆O₂Si
• 分子量: 242.434
• InChiKey: DJHIYZPUWYRQMF-FMIVXFBMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.93
• 重原子数：
  16.0
• 可旋转键数：
  6.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.77
• 拓扑面积：
  26.3
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  (E)-6-(tert-Butyl-dimethyl-silanyloxy)-2-methyl-hex-2-enal 在 盐酸 、 4-二甲氨基吡啶 、 disodium hydrogenphosphate 、 正丁基锂 、 三氟化硼乙醚 、 三乙胺 、 间氯过氧苯甲酸 、 三苯基膦 作用下， 以 四氢呋喃 、 乙醇 、 正己烷 、 二氯甲烷 为溶剂， 反应 6.17h， 生成 (2R*,3S*)-3-acetoxy-2-methyl-2-(2-trimethylsilyl)ethynyltetrahydropyran
  参考文献：
  名称：

  Co2(CO)8-mediated Endo Mode Cyclization of Epoxy-alcohol: Synthesis of 2-Ethynyl-3-hydroxy-2-methyltetrahydropyran and 2-Ethynyl-3-hydroxy-3-methyltetrahydropyran Derivatives.

  摘要：

  连续对4, 5-环氧-5-甲基-7-三甲基硅基-6-庚炔-1-醇在0 °C下与Co2(CO)8进行处理，并在−78 °C下加入催化量的BF3·OEt2，得到含有钴复合体的四氢吡喃衍生物。同样，4, 5-环氧-4-甲基-7-三甲基硅基-6-庚炔-1-醇在上述条件下发生环闭合，生成相应的四氢吡喃衍生物。在这些实验中观察到优先发生内环化而非外环化现象。

  DOI：

  10.1248/cpb.49.613
• 作为产物：
  描述：

  ethyl (E)-6-(tert-butyldimethylsiloxy)-2-methyl-2-hexenoate 在 草酰氯 、 二异丁基氢化铝 、 二甲基亚砜 、 三乙胺 作用下， 以 正己烷 、 二氯甲烷 为溶剂， 反应 1.0h， 生成 (E)-6-(tert-Butyl-dimethyl-silanyloxy)-2-methyl-hex-2-enal
  参考文献：
  名称：

  Co2(CO)8-mediated Endo Mode Cyclization of Epoxy-alcohol: Synthesis of 2-Ethynyl-3-hydroxy-2-methyltetrahydropyran and 2-Ethynyl-3-hydroxy-3-methyltetrahydropyran Derivatives.

  摘要：

  连续对4, 5-环氧-5-甲基-7-三甲基硅基-6-庚炔-1-醇在0 °C下与Co2(CO)8进行处理，并在−78 °C下加入催化量的BF3·OEt2，得到含有钴复合体的四氢吡喃衍生物。同样，4, 5-环氧-4-甲基-7-三甲基硅基-6-庚炔-1-醇在上述条件下发生环闭合，生成相应的四氢吡喃衍生物。在这些实验中观察到优先发生内环化而非外环化现象。

  DOI：

  10.1248/cpb.49.613

文献信息

• One-pot sequential cross-metathesis/hydride reduction: highly stereoselective synthesis of primary (E)-allylic alcohols from terminal olefins
  作者：Tapas Paul、Gopal Sirasani、Rodrigo B. Andrade

  DOI：10.1016/j.tetlet.2008.03.132

  日期：2008.5

  Several di- and trisubstituted primary (E)-allylic alcohols have been prepared from the corresponding terminal olefins in a highly stereoselective manner (>20:1 E/Z) by sequencing olefin cross-metathesis (CM) with hydride reduction (DIBAL-H) in good yields utilizing only commercially available reagents in a one-pot fashion. The method is a reliable alternative to the direct CM of terminal olefins with

  通过以氢化物还原法对烯烃交叉复分解（CM）进行测序（DIBAL-H），从相应的末端烯烃以高度立体选择性的方式（> 20：1 E / Z）制备了几种二和三取代的伯（E）烯丙基醇。）仅使用一锅法仅使用市售试剂即可获得高收率）。该方法是端烯与烯丙醇直接CM的可靠替代方法，后者并不总是立体选择性的，而是高度依赖底物的。
• Sequential cross-metathesis/phosphorus-based olefination: stereoselective synthesis of 2,4-dienoates
  作者：Tapas Paul、Rodrigo B. Andrade

  DOI：10.1016/j.tetlet.2007.06.031

  日期：2007.7

  A variety of stereodefined 2,4-dienoates have been prepared in a stereoselective manner by sequencing olefin cross-metathesis (CM) with phosphorus-based olefination reactions (Wittig and Horner–Wadsworth–Emmons) in good yield using commercially available reagents.

  通过使用可购得的试剂，以磷基烯烃化反应（Wittig和Horner-Wadsworth-Emmons）对烯烃交叉复分解（CM）进行测序，以立体选择性的方式制备了各种立体定义的2,4-二烯酸酯。
• An Approach to Cyclic α-Amino Acids by a Novel Hetero Diels-Alder/Intramolecular Hydantoin Enolate Alkylation Strategy: An Approach to Halichlorine
  作者：Deukjoon Kim、Hyoungsu Kim、Jae Hong Seo、Kye Jung Shin、Dong Jin Kim

  DOI：10.3987/com-06-s(w)43

  日期：——

  An efficient, novel synthetic strategy has been developed for preparation of cyclic α-amino acid employing an intermolecular hetero Diels-Alder reaction and an intramolecular hydantoin enolate alkylation as key steps. Application of the present hetero Diels-Alder/intramolecular hydantoin alkylation methodology to synthesis of halichlorine was explored.

  已经开发了一种有效的、新颖的合成策略来制备环状 α-氨基酸，采用分子间杂 Diels-Alder 反应和分子内乙内酰脲烯醇化物烷基化作为关键步骤。探索了本异Diels-Alder/分子内乙内酰脲烷基化方法在卤代氯合成中的应用。
• Sequencing cross-metathesis and non-metathesis reactions to rapidly access building blocks for synthesis
  作者：Gopal Sirasani、Tapas Paul、Rodrigo B. Andrade

  DOI：10.1016/j.tet.2011.01.080

  日期：2011.3

  The olefin cross-metathesis reaction has been sequenced with four common organic transformations in a one- or two-pot manner to rapidly access useful building blocks. Those reactions are: (1) phosphorus-based olefination (e.g.. Wittig and Horner-Wadsworth-Emmons); (2) hydride reduction; (3) Evans propionate aldol reaction; (4) Brown allyl- and Roush crotyl-boration. The products of these reactions include stereodefined 2,4-dienoates, trans allylic alcohols, syn-propionate aldols, and chiral non-racemic homoallylic alcohols, respectively. Many of these intermediates have been carried further to natural products, demonstrating the utility of the methodology. (C) 2011 Elsevier Ltd. All rights reserved.