2-{[(tert-butyldiphenylsilyl)oxy]methyl}-2(E)-butenal | 129144-88-3

• 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: 2-{[(tert-butyldiphenylsilyl)oxy]methyl}-2(E)-butenal
• 英文别名: (E)-2-[[tert-butyl(diphenyl)silyl]oxymethyl]but-2-enal
• CAS: 129144-88-3
• 化学式: C₂₁H₂₆O₂Si
• 分子量: 338.522
• InChiKey: WDTRRGOTMKNLJR-DVZOWYKESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.71
• 重原子数：
  24
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-{[(tert-butyldiphenylsilyl)oxy]methyl}-2(E)-butenal 在 咪唑 、 manganese(IV) oxide 、 草酰氯 、 2,6-二叔丁基-4-甲基苯酚 、 二异丁基氢化铝 、 potassium carbonate 、 二甲基亚砜 、 三乙胺 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 、 三氯乙烯 、 N,N-二甲基甲酰胺 为溶剂， 反应 16.0h， 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 、 manganese(IV) oxide 、 N-溴代丁二酰亚胺(NBS) 、 2,3-二巯基丁二酸 、 sodium acetate 、 二异丁基氢化铝 、 potassium carbonate 作用下， 以 乙醚 、 正己烷 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 99.0h， 生成 2-{[(tert-butyldiphenylsilyl)oxy]methyl}-2(E)-butenal
  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

• Enantioselective synthesis of the top half of chlorothricolide
  作者：William R. Roush、Richard J. Sciotti

  DOI：10.1016/s0040-4039(00)61260-1

  日期：1992.8

  Highly enantio- and diastereoselective syntheses of spirotetronates 4 and 5 corresponding to the top half of chlorothricolide are described.

  描述了对应于氯环硫内酯上半部分的螺酮酸酯4和5的高度对映体和非对映体选择性合成。
• Enantioselective Total Synthesis of (−)-Chlorothricolide via the Tandem Inter- and Intramolecular Diels−Alder Reaction of a Hexaenoate Intermediate
  作者：William R. Roush、Richard J. Sciotti

  DOI：10.1021/ja980611f

  日期：1998.8.1

  An enantioselective total synthesis of (−)-chlorothricolide (1) has been completed via a route involving the tandem inter- and intramolecular Diels−Alder (IMDA) reaction of hexaenoate 19 and the chiral dienophile (R)-12. This reaction, which establishes seven asymmetric centers in a single operation, is feasible only by virtue of the high diastereofacial and exo selectivity of dienophile 12. The C(9)-trimethylsilyl

  已经通过涉及六烯酸酯 19 和手性亲二烯体 (R)-12 的串联分子间和分子内 Diels-Alder (IMDA) 反应的路线完成了 (-)-氯三菌内酯 (1) 的对映选择性全合成。该反应在一次操作中建立了七个不对称中心，仅凭借亲二烯体 12 的高非对映面和外向选择性才可行。 19 的 C(9)-三甲基甲硅烷基空间定向基团也通过控制立体化学而发挥关键作用导致下半部分八氢化萘单元的 IMDA 反应过程。从已知的乙炔酮 33 开始，通过 10 步序列以 32% 的总收率制备了己烯酸酯 19。关键步骤包括使用高山硼烷（高达 94% ee）不对称还原 33，
• Studies on the Synthesis of Chlorothricolide:  Diastereo- and Enantioselective Syntheses of Model Top-Half Spirotetronate Units
  作者：William R. Roush、Richard J. Sciotti

  DOI：10.1021/jo980379w

  日期：1998.8.1

  Highly enantio- and diastereoselective syntheses of spirotetronates 9 and 10, corresponding to the top-half fragment of chlorothricolide, are described. Key steps in these syntheses are the Diels-Alder reactions of trienes 11 and 12 with the chiral dienophile (R)-6 that provide cycloadducts 18 and 38 with remarkably high stereoselectivity. These reactions exhibit exquisite regioselectivity for addition across the trisubstituted C(18)-C(21) diene unit; they also proceed with remarkable orientational control of the dienophile with respect to the C(18)-C(21) diene, as well as with excellent exo diastereofacial selectivity on the part of the chiral dienophile, (R)-6. Results are presented indicating that it is not necessary to control the stereochemistry of the C(20)-C(21) trisubstituted olefin of the triene precursors, as this unit :readily isomerizes under the conditions of the Diels-Alder reaction. Remarkably, the seemingly unreactive (E,E,E)-triene isomers (E,E,E)-11 and (E,E,E)-12 can be used as the starting material for the Diels-Alder reactions, and the desired exo-cycloadducts 18 and 38 are still obtained in good yield, without products of competitive Diels-Alder reactions of the disubstituted C(16)-C(19) dienes being observed.
• ROUSH, WILLIAM R.;BROWN, BRADLEY B., TETRAHEDRON LETT., 30,(1989) N2, C. 7309-7312
  作者：ROUSH, WILLIAM R.、BROWN, BRADLEY B.

  DOI：——

  日期：——