methyl (2E)-2-<<(tert-butyldiphenylsilyl)oxy>methyl>-2-butenoate | 146983-20-2

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: methyl (2E)-2-<<(tert-butyldiphenylsilyl)oxy>methyl>-2-butenoate
• 英文别名: (E)-methyl 2-(((tert-butyldiphenylsilyl)oxy)methyl)but-2-enoate；methyl (E)-2-[[tert-butyl(diphenyl)silyl]oxymethyl]but-2-enoate
• CAS: 146983-20-2
• 化学式: C₂₂H₂₈O₃Si
• 分子量: 368.548
• InChiKey: YLGQYGDEHVMBSB-NGYBGAFCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.68
• 重原子数：
  26
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  methyl (2E)-2-<<(tert-butyldiphenylsilyl)oxy>methyl>-2-butenoate 在 manganese(IV) oxide 、 二异丁基氢化铝 、 potassium carbonate 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 为溶剂， 生成 methyl (1S,2S,5R)-4-<<(tert-butyldiphenylsilyl)oxy>methyl>-1-hydroxy-5-methyl-2-<2'-methyl-3'-<(tert-butyldimethylsilyl)oxy>-1'(E)-propen-1'-yl>3-cyclohexene-1-carboxylate
  参考文献：
  名称：

  Kijanolide上半部分的非对映选择性合成

  摘要：

  描述了焦亚醇胺的上半部分（4）的高度非对映选择性的合成。关键步骤是三烯6和手性亲二烯体6的exo和非对映体选择性Diels-Alder反应。

  DOI：

  10.1016/s0040-4039(00)70684-8
• 作为产物：
  描述：

  3-羟基-2-亚甲基丁酸甲酯 在 咪唑 、 N-溴代丁二酰亚胺(NBS) 、 2,3-二巯基丁二酸 、 sodium acetate 、 potassium carbonate 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 50.0h， 生成 methyl (2E)-2-<<(tert-butyldiphenylsilyl)oxy>methyl>-2-butenoate
  参考文献：
  名称：

  A highly diastereo- and enantioselective synthesis of the top half of kijanolide

  摘要：

  A highly diastereo- and enantioselective synthesis of spirotetronate 4 corresponding to the top half of kijanolide is reported. This synthesis features the novel exo-selective Diels-Alder reaction of triene 6 and the chiral, nonracemic dienophiles (R)-7 and (R)-8. The reaction of 6 and (R)-7 produced a mixture of the desired exo cycloadduct 28, the unexpected exo diastereofacial isomer 29, and a minor amount of the endo cycloadduct 30. However, the Diels-Alder reaction of 6 and dienophile (R)-8 with the more sterically demanding tert-butyl substituent provided a 13-14:1 mixture of exo cycloadduct 38 and endo isomer 39; the exo diastereofacial isomer corresponding to 29 was not observed. Elaboration of 28 and 38 to spirotetronate 4 proceeded by way of the Dieckmann cyclization of alpha-acetoxy ester 5.

  DOI：

  10.1021/jo00060a035

文献信息

• Indium-mediated allylation of carbonyl compounds with an allylic bromide in aqueous media: anomalous syn-diastereoselectivity regardless of allylic bromide geometry
  作者：Teck-Peng Loh、Zheng Yin、Hong-Yan Song、Kee-Leng Tan

  DOI：10.1016/s0040-4039(02)02773-9

  日期：2003.1

  Anomalous syn-diastereoselectivity of indium-mediated coupling of aldehydes with bromides Z-3b and E-3b is reported. The reaction afforded high syn selectivity regardless of the allylic bromide geometry. Preliminary studies on the enantioselective indium-mediated allylation were attempted and found to give the desired products in moderate yield with high syn selectivity and enantioselectivity.

  异常顺醛与溴化物铟-介导的偶联的-diastereoselectivity ž -图3b和ë -图3b报道。不管烯丙基溴的几何形状如何，该反应均提供高的顺式选择性。尝试了对映选择性铟介导的烯丙基化的初步研究，发现以中等收率获得了所需的产物，同时具有高的顺式选择性和对映选择性。
• Diastereoselective synthesis of the top half of kijanolide
  作者：William R. Roush、Bradley B. Brown

  DOI：10.1016/s0040-4039(00)70684-8

  日期：1989.1

  A highly diastereoselective synthesis of the top half (4) of kijanolide is described. The key step is the exo and diastereoface selective Diels-Alder reaction of triene 6 and chiral dienophile 6.

  描述了焦亚醇胺的上半部分（4）的高度非对映选择性的合成。关键步骤是三烯6和手性亲二烯体6的exo和非对映体选择性Diels-Alder反应。
• Catalytic Enantioselective Total Synthesis of (+)-Torrubiellone C
  作者：Henning J. Jessen、Andreas Schumacher、Fabian Schmid、Andreas Pfaltz、Karl Gademann

  DOI：10.1021/ol201692h

  日期：2011.8.19

  Silyl-protected (R)-methyl 2-(hydroxymethyl)butanoate was obtained by an enantioselective Ir-catalyzed hydrogenation In high yield and selectivity. Elaboration of this building block via Takai and Stille reactions gave a protected hydroxy polyene chain, which was coupled to a 5-hydroxyphenyl-4-hydroxy-2-pyridone derivative by a modified Horner-Wadsworth-Emmons reaction. Deprotection gave synthetic (+)-torrublelione C, which led to the assignment of the configuration of the natural product as (R).
• A highly diastereo- and enantioselective synthesis of the top half of kijanolide
  作者：William R. Roush、Bradley B. Brown

  DOI：10.1021/jo00060a035

  日期：1993.4

  A highly diastereo- and enantioselective synthesis of spirotetronate 4 corresponding to the top half of kijanolide is reported. This synthesis features the novel exo-selective Diels-Alder reaction of triene 6 and the chiral, nonracemic dienophiles (R)-7 and (R)-8. The reaction of 6 and (R)-7 produced a mixture of the desired exo cycloadduct 28, the unexpected exo diastereofacial isomer 29, and a minor amount of the endo cycloadduct 30. However, the Diels-Alder reaction of 6 and dienophile (R)-8 with the more sterically demanding tert-butyl substituent provided a 13-14:1 mixture of exo cycloadduct 38 and endo isomer 39; the exo diastereofacial isomer corresponding to 29 was not observed. Elaboration of 28 and 38 to spirotetronate 4 proceeded by way of the Dieckmann cyclization of alpha-acetoxy ester 5.