(1E,4'S)-3-[(tert-Butyldiphenylsilyl)oxy]-1-(2',2'-dimethyl-1',3'-dioxolan-4'-yl)-1-propene | 154001-54-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1E,4'S)-3-[(tert-Butyldiphenylsilyl)oxy]-1-(2',2'-dimethyl-1',3'-dioxolan-4'-yl)-1-propene
• 英文别名: tert-butyl-[(E)-3-[(4S)-2,2-dimethyl-1,3-dioxolan-4-yl]prop-2-enoxy]-diphenylsilane
• CAS: 154001-54-4
• 化学式: C₂₄H₃₂O₃Si
• 分子量: 396.602
• InChiKey: WLDKWOPSIIGROC-SJFMBGHLSA-N

物化性质

• 沸点：
  445.6±45.0 °C(Predicted)
• 密度：
  1.05±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.27
• 重原子数：
  28
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (1E,4'S)-3-[(tert-Butyldiphenylsilyl)oxy]-1-(2',2'-dimethyl-1',3'-dioxolan-4'-yl)-1-propene 在 Candia cylindracea lipase 四丁基氟化铵 、 diethylzinc 、 2-碘酰基苯甲酸 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 、 二氯甲烷 、 二甲基亚砜 为溶剂， 生成 [(1R)-1-[(1R,2R)-2-[(4S)-2,2-dimethyl-1,3-dioxolan-4-yl]cyclopropyl]but-3-enyl] acetate
  参考文献：
  名称：

  关于苏糖内酯总合成的研究：环丙烷-内酯链段的立体选择性合成

  摘要：

  已经开发了一种简单的立体选择路线，以合成茄醛酸内酯的右手片段，在该方法中，首先合成关键的双功能环丙烷中间体2，然后以良好的总收率构建了八元内酯环。

  DOI：

  10.1016/s0040-4039(97)10731-6
• 作为产物：
  描述：

  (S)-(+)-3-(2,2-二甲基-1,3-二噁戊环-4-基)-反-2-丙烯酸甲酯 在 咪唑 、 二异丁基氢化铝 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 生成 (1E,4'S)-3-[(tert-Butyldiphenylsilyl)oxy]-1-(2',2'-dimethyl-1',3'-dioxolan-4'-yl)-1-propene
  参考文献：
  名称：

  Evaluation of possible intramolecular [4+2] cycloaddition routes for assembling the central tetracyclic core of the potent marine antiinflammatory agent mangicol A

  摘要：

  A plan for enantioselective construction of the mangicol A framework by means of intramolecular Diels-Alder cycloaddition is outlined. First to be assembled is the enantiopure cyclopentenecarboxylic acid 16. Of the several approaches targeting the 1,3-diene component 56, only that involving palladium-catalyzed enyne cyclization proved successful. Following the coupling of 16 to 56, we were unable to bring about any detectable level of (4 pi+2 pi) cycloaddition. Activation of the diene by incorporation of an OSiEt3 substituent on a terminal sp(2)-hybridized center likewise proved unsuccessful. Further facilitation was sought in the form of cyclopentenonecarboxylate 66. However, thermal activation, Lewis acid catalysis, and high-pressure conditions proved ineffective and did not lead to C-C bond formation. These studies serve to underscore the extent to which steric complications can complicate matters and the extent to which they must be skirted to arrive at the title compound. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2005.11.096

文献信息

• On stereochemistry of osmium tetraoxide oxidation of allylic alcohol systems. Empirical rule
  作者：J.K. Cha、W.J. Christ、Y. Kishi

  DOI：10.1016/0040-4020(84)80008-3

  日期：1984.1

  An empirical formulation is presented to predict the stereochemistry of major osmylation products of allylic alcohols and their derivatives.

  提出了一种经验公式来预测烯丙基醇及其衍生物的主要渗透作用产物的立体化学。
• Efficient Acyclic Stereocontrol Using the Tethered Aminohydroxylation Reaction
  作者：Timothy J. Donohoe、Peter D. Johnson、Richard J. Pye、Martine Keenan

  DOI：10.1021/ol049136i

  日期：2004.7.1

  [reaction: see text] The tethered aminohydroxylation (TA) of acyclic allylic carbamates has been achieved in a stereospecific and stereoselective manner. Unusually high levels of stereocontrol were observed in the oxidation of 1,1-disubstituted substrates.

  [反应：见正文]非环状烯丙基氨基甲酸酯的束缚氨基羟基化（TA）已通过立体定向和立体选择性方式实现。在1，1-二取代的底物的氧化中观察到异常高水平的立体控制。
• Stereoselective synthesis of the C1C10 fragment of constanolactones A and B
  作者：Sundararaman Varadarajan、Debendra K Mohapatra、Apurba Datta

  DOI：10.1016/s0040-4039(98)01103-4

  日期：1998.7

  An efficient synthesis of the cyclopropyl-lactone containing right hand fragment (C1C10) of the title constanolactones has been developed starting from an easily available (S)-glyceraldehyde derivative 4.

  含有右手片段环丙基内酯的有效合成（C 1 C 10）的标题constanolactones已经开发从容易获得的（起始小号）甘油醛衍生物4。
• Synthesis of optically active cis- and trans-1,2-disubstituted cyclopropane derivatives by the Simmons-Smith reaction of allyl alcohol derivatives derived from (R)-2,3-O-isopropylideneglyceraldehyde
  作者：Tsutomu Morikawa、Hirofumi Sasaki、Ryo Hanai、Akira Shibuya、Takeo Taguchi

  DOI：10.1021/jo00080a017

  日期：1994.1

  The Simmons-Smith reactions of Z- and E-allyl alcohol derivatives 6 derived from (R)-2,3-O-isopropylideneglyceraldehyde (5) were used for the synthesis of optically active cis- and trans-1,2 disubstituted cyclopropane derivatives. Reaction of 6 with diethyl zinc and diiodomethane gave cyclopropane derivatives 7 in 84% to quantitative yields with 35 to approximate to 100% des. Identical facial selectivities toward the double bonds, Ire-asi for Z-6 and 1re-2re for E-6, were observed in the cyclopropanations. The diastereoselectivity was dependent on the protecting group on the terminal allylic oxygen (R of 6, TBDPS > MOM > Bn) and on the stereochemistry of the double bond (Z > E). For TBDPS ethers Z- and E-6c, cis- and trans-7c were obtained as single diastereomers respectively. It was clearly demonstrated that the stereoselectivity of the cyclopropanation is controlled by the directing effect of the allylic oxygen (O-1) of the dioxolane ring which coordinates to the reagent. The terminal allylic oxygen (O-2) lowered the diastereoselectivity This reaction was applied to the synthesis of optically active cyclopropane analogs of gamma-aminobutyric acid (GABA) 18, 22, and ent-22.
• Evaluation of possible intramolecular [4+2] cycloaddition routes for assembling the central tetracyclic core of the potent marine antiinflammatory agent mangicol A
  作者：Stefan Pichlmair、Manuel de Lera Ruiz、Kallol Basu、Leo A. Paquette

  DOI：10.1016/j.tet.2005.11.096

  日期：2006.5

  A plan for enantioselective construction of the mangicol A framework by means of intramolecular Diels-Alder cycloaddition is outlined. First to be assembled is the enantiopure cyclopentenecarboxylic acid 16. Of the several approaches targeting the 1,3-diene component 56, only that involving palladium-catalyzed enyne cyclization proved successful. Following the coupling of 16 to 56, we were unable to bring about any detectable level of (4 pi+2 pi) cycloaddition. Activation of the diene by incorporation of an OSiEt3 substituent on a terminal sp(2)-hybridized center likewise proved unsuccessful. Further facilitation was sought in the form of cyclopentenonecarboxylate 66. However, thermal activation, Lewis acid catalysis, and high-pressure conditions proved ineffective and did not lead to C-C bond formation. These studies serve to underscore the extent to which steric complications can complicate matters and the extent to which they must be skirted to arrive at the title compound. (c) 2006 Elsevier Ltd. All rights reserved.