(1Z,3E)-1-(tert-butyldimethylsiloxy)-1-methoxypenta-1,3-diene | 172658-39-8

• 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
• 英文名称: (1Z,3E)-1-(tert-butyldimethylsiloxy)-1-methoxypenta-1,3-diene
• 英文别名: (1Z,3E)-1-(t-butyldimethylsilyloxy)-1-methoxypenta-1,3-diene；tert-butyl-[(1Z,3E)-1-methoxypenta-1,3-dienoxy]-dimethylsilane
• CAS: 172658-39-8
• 化学式: C₁₂H₂₄O₂Si
• 分子量: 228.407
• InChiKey: JLQYAEJCAVLHKV-OCBXPSTGSA-N

物化性质

• 沸点：
  240.1±23.0 °C(Predicted)
• 密度：
  0.871±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.07
• 重原子数：
  15
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 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：

  (1Z,3E)-1-(tert-butyldimethylsiloxy)-1-methoxypenta-1,3-diene 在 四氯苯醌 作用下， 以 二氯甲烷 为溶剂， 以76%的产率得到methyl (2E)-penta-2,4-dienoate
  参考文献：
  名称：

  摘要：

  Reaction of certain geometrically defined 1,1-dioxy-4-alkyl- and -4,4-dialkyl-substituted buta-1,3-dienes with halogenated quinones does not involve Diels-Alder or Michael addition chemistry. Instead, rapid competitive oxidation of the dienes to give 2,4-dienoate esters was observed. This new reaction involves strong spatial association between diene and quinone, hydrogen being transferred specifically from the (4E)-alkyl group. Its scope is compared with addition of the same terminally substituted dienes towards the reactive non-quinonoid dienophile tetracyanoethylene.

  DOI：

  10.1071/ch00027
• 作为产物：
  描述：

  methyl cis-2-pentenoate 、 叔丁基二甲基氯硅烷 在 六甲基磷酰三胺 、 正丁基锂 、 二异丙胺 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 0.67h， 以48%的产率得到(1Z,3E)-1-(tert-butyldimethylsiloxy)-1-methoxypenta-1,3-diene
  参考文献：
  名称：

  摘要：

  Reaction of certain geometrically defined 1,1-dioxy-4-alkyl- and -4,4-dialkyl-substituted buta-1,3-dienes with halogenated quinones does not involve Diels-Alder or Michael addition chemistry. Instead, rapid competitive oxidation of the dienes to give 2,4-dienoate esters was observed. This new reaction involves strong spatial association between diene and quinone, hydrogen being transferred specifically from the (4E)-alkyl group. Its scope is compared with addition of the same terminally substituted dienes towards the reactive non-quinonoid dienophile tetracyanoethylene.

  DOI：

  10.1071/ch00027

文献信息

• Highly Diastereoselective Three-Component Vinylogous Mannich Reaction between Isoquinolines, Acyl/Sulfonyl Chlorides, and Silyloxyfurans
  作者：Philippe Hermange、Marie Elise Tran Huu Dau、Pascal Retailleau、Robert H. Dodd

  DOI：10.1021/ol901452d

  日期：2009.9.17

  Reaction of an isoquinoline, a silyloxyfuran, and an acyl or sulfonyl chloride provides easy access to a wide variety of isoquinolinobutyrolactones with excellent yields and diastereoselectivites (R*,R* isomer), even in the case of formation of quaternary centers (i.e., R3 or R4 = Me). Moreover, the use of a chiral auxiliary allowed formation of a single stereoisomer in 96% yield. This represents the

  异喹啉，一个silyloxyfuran，和酰基或磺酰氯的反应提供方便各种具有优异的产率和diastereoselectivites（isoquinolinobutyrolactones的R *，R *异构体），即使是在形成季中心（即，R的情况下3或R 4 = Me）。此外，使用手性助剂可以形成单一立体异构体，产率为96％。这代表了异喹啉鎓盐上不对称乙烯基曼尼希反应的第一个例子。
• Enolisation of αβ-unsaturated esters : regio- and geometrical control
  作者：Donald W. Cameron、Mark G. Looney、Judy A. Pattermann

  DOI：10.1016/0040-4039(95)01531-0

  日期：1995.10

  LDA-Mediated γ-deprotonation of simple αβ-unsaturated esters occurs (Z)- to the ester group; silylation then leads to oxy butadienes with strong regio- and geometrical selectivity.

  LDA介导的简单αβ-不饱和酯的γ去质子化反应发生在酯基上（Z）-；然后，甲硅烷基化会产生具有强烈的区域和几何选择性的氧丁二烯。
• Rapid Access to Polyketide Scaffolds via Vinylogous Mukaiyama Aldol Reactions
  作者：Jorma Hassfeld、Mathias Christmann、Markus Kalesse

  DOI：10.1021/ol016677o

  日期：2001.11.1

  [reaction: see text]. The use of the Z-configured vinylogous silyl ketene acetals in Mukaiyama aldol reactions is described. Isopropyl alcohol as scavanger and the use of tris(pentafluorophenyl)borane as the Lewis acid are required for obtaining the gamma-alkylated syn-product selectively. In cases of alpha-chiral aldehydes, Felkin-Anh selectivity was observed.

  [反应：请参见文字]。描述了Z构型的乙烯基硅烷基乙烯酮缩醛在Mukaiyama羟醛反应中的用途。为了选择性地获得γ-烷基化的合成产物，需要异丙醇作为稀溶剂，并使用三（五氟苯基）硼烷作为路易斯酸。在α-手性醛的情况下，观察到Felkin-Anh选择性。
• A One-Pot Non-Aldol-Aldol Vinylogous Mukaiyama Aldol Tandem Sequence for the Rapid Construction of Polyketide Frameworks
  作者：Markus Kalesse、Nicola Rahn

  DOI：10.1055/s-2005-863743

  日期：——

  The rapid assembly of polyketide segments remains one central task in the field of natural product synthesis. Besides the ­stereoselective assembly of carbon frameworks functional group transformations and protecting group manipulations have to be ­optimized in order to streamline organic synthesis. The activated ­aldehyde derived from Jung’s non aldol-aldol method serves as an intermediate for the subsequent vinylogous Mukaiyama aldol ­reaction.

  快速组装多酮片段仍然是天然产物合成领域的一项核心任务。除了立体选择性组装碳框架外，还必须优化官能团转化和保护基操作，以简化有机合成。从 Jung 的非醛-醛醇法中得到的活化醛是随后的乙烯基 Mukaiyama 醛醇反应的中间体。
• ——
  作者：Donald W. Cameron、Ross M. Heisey

  DOI：10.1071/ch00027

  日期：——

  Reaction of certain geometrically defined 1,1-dioxy-4-alkyl- and -4,4-dialkyl-substituted buta-1,3-dienes with halogenated quinones does not involve Diels-Alder or Michael addition chemistry. Instead, rapid competitive oxidation of the dienes to give 2,4-dienoate esters was observed. This new reaction involves strong spatial association between diene and quinone, hydrogen being transferred specifically from the (4E)-alkyl group. Its scope is compared with addition of the same terminally substituted dienes towards the reactive non-quinonoid dienophile tetracyanoethylene.