(E,Z)-3-<(tert-butyldimethylsilyl)oxy>-1-methoxy-2-methyl-1,3-pentadiene | 98703-75-4

• 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,Z)-3-<(tert-butyldimethylsilyl)oxy>-1-methoxy-2-methyl-1,3-pentadiene
• 英文别名: (E,Z)-3-[(tert-butyldimethylsilyl)oxy]-1-methoxy-2-methyl-1,3-pentadiene；tert-butyl-[(1E,3Z)-1-methoxy-2-methylpenta-1,3-dien-3-yl]oxy-dimethylsilane
• CAS: 98703-75-4
• 化学式: C₁₃H₂₆O₂Si
• 分子量: 242.434
• InChiKey: BERBUCORUYUNLF-MWOVLNQWSA-N

物化性质

• 沸点：
  70-85 °C(Press: 1.0 Torr)
• 密度：
  0.870±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.46
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.69
• 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,Z)-3-<(tert-butyldimethylsilyl)oxy>-1-methoxy-2-methyl-1,3-pentadiene 在 sodium tetrahydroborate 、 cerium(III) chloride 、 三氟化硼乙醚 、 4-甲基苯磺酸吡啶 、 对甲苯磺酸 作用下， 以 乙醇 、 二氯甲烷 、 苯 为溶剂， 反应 3.67h， 生成 <2S-<2α(2R*,3S*,4R*),3β,6β>>-<<4-<3,6-Dihydro-3,5-dimethyl-6-(1-methylethoxy)-2H-pyran-2-yl>-2-methyl-3-(phenylmethoxy)pentyl>oxy>(1,1-dimethylethyl)diphenylsilane (Pyran 13)
  参考文献：
  名称：

  Development of a fully synthetic stereoselective route to 6-deoxyerythronolide B by reiterative applications of the Lewis acid catalyzed diene aldehyde cyclocondensation reaction: a remarkable instance of diastereofacial selectivity

  摘要：

  DOI：

  10.1021/jo00292a045
• 作为产物：
  描述：

  (E)-1-methoxy-2-methylpent-1-en-3-one 、 叔丁基二甲硅基三氟甲磺酸酯 在 三乙胺 作用下， 以 乙醚 为溶剂， 反应 3.0h， 以91%的产率得到(E,Z)-3-<(tert-butyldimethylsilyl)oxy>-1-methoxy-2-methyl-1,3-pentadiene
  参考文献：
  名称：

  Variations in the stereochemistry of the boron trifluoride mediated cyclocondensation reaction of aldehydes with siloxy dienes

  摘要：

  DOI：

  10.1021/jo00223a049

文献信息

• Asymmetric hetero Diels–Alder reaction of Danishefsky's dienes and glyoxylates with chiral bis(oxazolinyl)phenylrhodium(III) aqua complexes, and its mechanistic studies
  作者：Yukihiro Motoyama、Yoshiyuki Koga、Hisao Nishiyama

  DOI：10.1016/s0040-4020(00)01049-8

  日期：2001.1

  Asymmetric hetero Diels–Alder reaction of Danishefsky's dienes with glyoxylates is catalyzed in high enantioselectivity and cis (endo)-diastereoselectivity by chiral (Phebox)RhCl2(H2O) complexes [Phebox=2,6-bis(oxazolinyl)phenyl], via the concerted [4+2] mechanism with perpendicular conformation of two carbonyl moieties of glyoxylates. Dibromide and difluoride complexes were newly synthesized and found

  Danishefsky二烯与乙醛酸酯的不对称杂Diels-Alder反应通过手性（Phebox）RhCl 2（H 2 O）络合物[Phebox = 2,6-双（恶唑啉基）苯基]催化高对映选择性和顺（内）-非对映选择性。通过一致的[4 + 2]机理与乙醛酸酯的两个羰基部分的垂直构象。新合成了二溴化物和二氟化物配合物，发现杂Diels–Alder产物的对映选择性比母体二氯化物配合物略高（Cl：80％ee，Br：82％ee，F：84％ee）。
• The Dihydropyrone Diels–Alder Reaction: Development and Application to the Synthesis of Highly Functionalized 1-Oxa-4-decalones
  作者：Punit P. Seth、Deqi Chen、Junquan Wang、Xiuchun Gao、Nancy I. Totah

  DOI：10.1016/s0040-4020(00)00863-2

  日期：2000.12

  A facile method for the synthesis of highly functionalized 1-oxadecalone derivatives is described via the Diels–Alder reaction of 2,3-dihydro-4-pyrone dienophiles with electron rich dienes. By this process a variety of functional groups and substitution patterns can be incorporated into the oxadecalone framework.

  通过2，3-二氢-4-吡喃二烯亲二烯体与富电子二烯的Diels-Alder反应，描述了一种合成高度官能化的1-oxadecalone衍生物的简便方法。通过该过程，可以将各种官能团和取代模式结合到奥沙德考尼框架中。
• Efficient <i>trans</i>-Selectivity in the Cyclocondensation of (<i>S</i>)-2-[2-(<i>p</i>-Tolylsulfinyl)phenyl]acetaldehyde with Activated Dienes Catalyzed by Yb(OTf)₃
  作者：José L. García Ruano、M. Ángeles Fernández-Ibáñez、M. Carmen Maestro

  DOI：10.1021/jo061128n

  日期：2006.9.1

  Reactions of (S)-2-[2-(p-tolylsulfinyl)phenyl]acetaldehyde 1 with Danishefsky's and related dienes took place in the presence of Yb(OTf)(3) in a completely stereoselective manner, mediated by a remote sulfinyl group (1,5-asymmetric induction), to afford the corresponding 2,3-dihydro-4H-pyran-4-ones. These reactions followed a stepwise mechanism, as was corroborated by isolation of the corresponding intermediates, with a high level of trans-selectivity for 4-methyl-substituted dienes. Treatment of the adducts with Raney Ni provided concomitant cleavage of the C-S bond and reduction of the conjugated carbonyl grouping.
• Diastereoselective cyclocondensation of electron-rich dienes with chiral thio-substituted aldehydes
  作者：Rita Annunziata、Mauro Cinquini、Franco Cozzi、Pier Giorgio Cozzi、Laura Raimondi

  DOI：10.1021/jo00039a019

  日期：1992.6

  The Lewis acid-promoted cyclocondensation between two electron -rich dienes with a series of racemic alpha- and beta-thio-substituted aldehydes has been studied. Boron trifluoride etherate proved to be the catalyst of choice, affording satisfactory chemical yields and generally good diastereoselectivities. Other Lewis acidic catalysts gave lower yields and in some cases reversed the sense of the diastereoselection. A rationalization of the stereochemical results is presented.
• On the Stereochemistry of the Dihydropyrone Diels−Alder Reaction
  作者：Punit P. Seth、Nancy I. Totah

  DOI：10.1021/ol9909637

  日期：1999.11.1

  [GRAPHICS]The Diels-Alder reaction of activated dihydropyrones with electron-rich dienes proceeds with synthetically useful levels of diastereoselectivity Product ratios vary with the nature and location of substituents on diene and dienophile, as well as with reaction conditions. Lewis acid catalyzed reactions of related pyrone and benzopyrone dienophiles are also diastereoselective.