(E)-1-(Benzyloxy)-4-<(tert-butyldimethylsilyl)oxy>-2-butene | 151359-19-2

• 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: (E)-1-(Benzyloxy)-4-<(tert-butyldimethylsilyl)oxy>-2-butene
• 英文别名: (E)-1-(benzyloxy)-4-[(tert-butyldimethylsilyl)-oxy]-2-butene；trans-1-(benzyloxy)-4-(t-butyldimethylsilyloxy)-2-butene；(E)-4-benzyloxy-2-butenyl tert-butyldimethylsilyl ether；tert-butyl-dimethyl-[(E)-4-phenylmethoxybut-2-enoxy]silane
• CAS: 151359-19-2
• 化学式: C₁₇H₂₈O₂Si
• 分子量: 292.494
• InChiKey: ODRAJAVKOVULMH-MDZDMXLPSA-N

物化性质

• 沸点：
  340.4±30.0 °C(Predicted)
• 密度：
  0.934±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.78
• 重原子数：
  20
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.53
• 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)-1-(Benzyloxy)-4-<(tert-butyldimethylsilyl)oxy>-2-butene 在 草酰氯 、 sodium 、 二甲基亚砜 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 氨 为溶剂， 反应 0.33h， 生成 (E)-4-((tert-butyldimethylsilyl)oxy)but-2-enal
  参考文献：
  名称：

  Asymmetric Synthesis of Thietanose

  摘要：

  Syntheses of optically active thietanose, (2R,3R,4R)-4-acetoxymethyl-3-(tert-butyldimethylsilyl)oxy-2-ethoxythietane (6) and (2R,3R,4R)-3-(tertbutyldimethylsilyl)oxy-4-[(tert-butyldimethylsilyl)oxy]methyl-2-ethoxythietane (23) are described. The key intermediate, (2S,3S)-4,4-bis(ethoxy)-3-(tertbutyldimethylsilyl)oxy-1,2-epithiobutane (7) has been derived from (Z)-2-butene-1,4-diol in 13 steps. Although direct transformation of 7 to thietanose (6) failed, regio and stereospecific ring opening of the episulfide ring in 7 and acid catalyzed cyclization of the resulting 3-mercaptobutanal diethyl acetal (20) was successful in forming of a thietane ring to give 6. The structure of 6 and 23 was confirmed by spectroscopic analyses including NOE experiments.

  DOI：

  10.3987/com-97-s(n)67
• 作为产物：
  描述：

  顺-4-苄氧基-2-丁烯-1-醇 在 咪唑 、 sodium tetrahydroborate 、 草酰氯 、 二甲基亚砜 、 三乙胺 作用下， 以 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 1.08h， 生成 (E)-1-(Benzyloxy)-4-<(tert-butyldimethylsilyl)oxy>-2-butene
  参考文献：
  名称：

  Asymmetric Synthesis of Thietanose

  摘要：

  Syntheses of optically active thietanose, (2R,3R,4R)-4-acetoxymethyl-3-(tert-butyldimethylsilyl)oxy-2-ethoxythietane (6) and (2R,3R,4R)-3-(tertbutyldimethylsilyl)oxy-4-[(tert-butyldimethylsilyl)oxy]methyl-2-ethoxythietane (23) are described. The key intermediate, (2S,3S)-4,4-bis(ethoxy)-3-(tertbutyldimethylsilyl)oxy-1,2-epithiobutane (7) has been derived from (Z)-2-butene-1,4-diol in 13 steps. Although direct transformation of 7 to thietanose (6) failed, regio and stereospecific ring opening of the episulfide ring in 7 and acid catalyzed cyclization of the resulting 3-mercaptobutanal diethyl acetal (20) was successful in forming of a thietane ring to give 6. The structure of 6 and 23 was confirmed by spectroscopic analyses including NOE experiments.

  DOI：

  10.3987/com-97-s(n)67

文献信息

• Arabinose-Derived Ketones as Catalysts for Asymmetric Epoxidation of Alkenes
  作者：Tony K. M. Shing、Gulice Y. C. Leung、To Luk

  DOI：10.1021/jo050928f

  日期：2005.9.1

  Readily available arabinose-derived ketones, containing a tunable butane-2,3-diacetal as the steric blocker, displayed increasing enantioselectivity (up to 90% ee) with the size of the acetal alkyl group in catalytic asymmetric epoxidation of trans-disubstituted and trisubstituted alkenes. The stereochemical communication between our ketone catalysts and the alkene substrates is mainly due to steric

  现成的阿拉伯糖衍生的酮，包含可调节的2,3-丁烷作为空间阻滞剂，在反式-二取代和三取代的催化不对称环氧化反应中，随着乙缩醛烷基大小的增加，对映选择性增加（最多90％ee）。烯烃。我们的酮催化剂与烯烃底物之间的立体化学连通主要是由于空间效应，而涉及底物和催化剂的苯基之间的π-π相互作用的电子效应在我们的系统中似乎不起作用。
• Efficient and Stereoselective Synthesis of Allylic Ethers and Alcohols
  作者：Jiří Pospíšil、István E. Markó

  DOI：10.1021/ol062433y

  日期：2006.12.1

  [Structure: see text] A short and efficient synthesis of allylic TBS ethers and allylic alcohols has been developed, based upon a unique Kocienski-Julia olefination reaction. Allylic alcohols and allylic ethers are obtained in good to excellent yields and with high (E)-selectivity. The conditions are mild and the procedure is broadly applicable.

  [结构：见正文]基于独特的Kocienski-Julia烯化反应，开发了一种短而有效的烯丙基TBS醚和烯丙基醇的合成方法。获得烯丙基醇和烯丙基醚的产率高至优异，并且具有高（E）-选择性。条件温和，程序可广泛应用。
• Regiochemical control of the ring opening of 1:2-epoxides by means of chelating processes. 10. Synthesis and ring opening reactions of mono- and difunctionalized cis and trans aliphatic oxirane systems
  作者：Francesca Azzena、Federico Calvani、Paolo Crotti、Cristina Gardelli、Franco Macchia、Mauro Pineschi

  DOI：10.1016/0040-4020(95)00633-j

  日期：1995.9

  The regiochemical outcome of the ring opening of 1:2-epoxides through chelation processes assisted by metal ions, was verified in mono- and difunctionalized aliphatic oxirane systems bearing the heterofunctionality (OR) in an homoallylic and/or allylic relationship to the oxirane ring. The effect of the distance of the OR functionality from the oxirane ring and of the type of protective group on the

  通过单官能和双官能的脂族环氧乙烷体系在与环氧乙烷环呈均烯丙基和/或烯丙基关系的杂官能度（OR）中验证了通过金属离子辅助的螯合过程使1：2-环氧化物开环的区域化学结果。检查了OR官能团与环氧乙烷环的距离以及保护基类型对这些系统的区域化学结果的影响。在某些情况下，使用LiClO 4或Mg（ClO 4）2作为促进金属盐使得有可能获得良好的区域交替方法。
• Efficient chemoselective deprotection of silyl ethers using catalytic 1-chloroethyl chloroformate in methanol
  作者：Chang-Eun Yeom、Young Jong Kim、So Young Lee、Yong Je Shin、B. Moon Kim

  DOI：10.1016/j.tet.2005.10.043

  日期：2005.12

  Fast and chemoselective desilylation of silyl-protected alcohols was achieved using a catalytic amount of 1-chloroethyl chloroformate in methanol. With a minimal amount of 1-chloroethyl chloroformate as the source for anhydrous HCl, extremely efficient cleavage of silyl ethers of primary and secondary alcohols was accomplished, and chemoselective deprotection of one silyl ether in the presence of another silyl or other acid-labile group was possible through controlling the amount of the chloroformate and reaction time. (c) 2005 Elsevier Ltd. All rights reserved.
• An Access to erythro-Diols via Sharpless's Asymmetric Dihydroxylation Reaction
  作者：Soo Y. Ko、Majbeen Malik、A. Frances Dickinson

  DOI：10.1021/jo00088a045

  日期：1994.5

  A method has been developed to access erythro-2,3-diols via Sharpless's asymmetric dihydroxylation reaction. Thus, a TBDMS-protected (E)-allylic alcohol is dihydroxylated and the resulting threo-2,3-diol is converted to the cyclic sulfate. Upon desilylation, this compound undergoes a Payne-type rearrangement. Nucleophilic epoxide-opening then provides an erythro-2,3-diol. The conversions from the cyclic sulfate to the diol product are performed in a single reaction vessel. Due to the irreversible nature of the Payne-type rearrangement, this process is easy to perform and completely regioselective independent of the substrate structures. Also, being performed in THF, the process is compatible with a variety of nucleophiles, including thiolates, N--(3), (OAc)-O--, (CN)-C--, halides as well as carbon nucleophiles and hydride.