(E)-16-iodo-1,5-hexadecadiene-7,9-diyne | 218965-28-7

• 分子结构分类: 有机化合物 - 乙炔化物
• 英文名称: (E)-16-iodo-1,5-hexadecadiene-7,9-diyne
• 英文别名: (5E)-16-iodohexadeca-1,5-dien-7,9-diyne
• CAS: 218965-28-7
• 化学式: C₁₆H₂₁I
• 分子量: 340.247
• InChiKey: NRGYUAKUOYXEHT-AATRIKPKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.8
• 重原子数：
  17
• 可旋转键数：
  9
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  cis-4,5-dihydro-4-hydroxy-5-methyl-2(3H)-furanone 、 (E)-16-iodo-1,5-hexadecadiene-7,9-diyne 在 lithium diisopropyl amide 作用下， 生成 (3S,4S,5S)-3-(11,15-hexadecadiene-7,9-diynyl)-4,5-dihydro-4-hydroxy-5-methyl-2(3H)-furanone 、 (3R,4R,5R)-3-(11,15-hexadecadiene-7,9-diynyl)-4,5-dihydro-4-hydroxy-5-methyl-2(3H)-furanone
  参考文献：
  名称：

  Total Syntheses of (−)-Grandinolide and (−)-Sapranthin by the Sharpless Asymmetric Dihydroxylation of Methyltrans-3-Pentenoate: Elucidation of the Stereostructure of (−)-Sapranthin

  摘要：

  Methyl trans-3-pentenoate (7) was converted into the cis-substituted gamma-lactone 8 in a single step with 78 % ee. The derived enolate dilithio-8 was alkylated trans-selectively with primary iodoalkanes. with 1-iodobutane dilithio-8 afforded, after esterification with isovaleroyl chloride, the epi-blast mycinone 9, Dilithio-8 gave (-)-grandinolide (11) with 1-iodo-19-phenylnonadecane (20), A third trans-selective alkylation of dilithio-8 was undertaken with 16-iodo-1.5-hexadecadiene-7,9-diyne (21). This gave the gamma-lactone 12. which had the published relative configuration of (-)-sapranthin but different spectroscopic data, When the OH group of lactone 8 was inverted (to hydroxylactone 40) and the derived enolate dilithio-40 alkylated with iodide 21, lactone 41 resulted, Its H-1 and C-13 NMR spectra and the sign and value of optical rotation coincide with the data of natural sapranthin, These findings establish that (-)-sapranthin possesses the relative and absolute configuration of stereoformula 41. The synthesis of iodide 21 was performed via the dienoic carboxylic ester trans-23 which stemmed from the Claisen-Ireland rearrangement (27 --> 28/29)/esterification (28/29 --> 26)/Cope rearrangement (26 - 23) sequence shown in Scheme 5.

  DOI：

  10.1002/(sici)1521-3765(19981102)4:11<2342::aid-chem2342>3.0.co;2-q
• 作为产物：
  描述：

  (E)-8-bromo-1,5-octadiene-7-yne 在 bis(dibenzylideneacetone)-palladium⁽⁰⁾ 1,2,2,6,6-五甲基哌啶 、 咪唑 、 copper(l) iodide 、 碘 、 三苯基膦 、 lithium iodide 作用下， 以 四氢呋喃 为溶剂， 反应 3.17h， 生成 (E)-16-iodo-1,5-hexadecadiene-7,9-diyne
  参考文献：
  名称：

  Total Syntheses of (−)-Grandinolide and (−)-Sapranthin by the Sharpless Asymmetric Dihydroxylation of Methyltrans-3-Pentenoate: Elucidation of the Stereostructure of (−)-Sapranthin

  摘要：

  Methyl trans-3-pentenoate (7) was converted into the cis-substituted gamma-lactone 8 in a single step with 78 % ee. The derived enolate dilithio-8 was alkylated trans-selectively with primary iodoalkanes. with 1-iodobutane dilithio-8 afforded, after esterification with isovaleroyl chloride, the epi-blast mycinone 9, Dilithio-8 gave (-)-grandinolide (11) with 1-iodo-19-phenylnonadecane (20), A third trans-selective alkylation of dilithio-8 was undertaken with 16-iodo-1.5-hexadecadiene-7,9-diyne (21). This gave the gamma-lactone 12. which had the published relative configuration of (-)-sapranthin but different spectroscopic data, When the OH group of lactone 8 was inverted (to hydroxylactone 40) and the derived enolate dilithio-40 alkylated with iodide 21, lactone 41 resulted, Its H-1 and C-13 NMR spectra and the sign and value of optical rotation coincide with the data of natural sapranthin, These findings establish that (-)-sapranthin possesses the relative and absolute configuration of stereoformula 41. The synthesis of iodide 21 was performed via the dienoic carboxylic ester trans-23 which stemmed from the Claisen-Ireland rearrangement (27 --> 28/29)/esterification (28/29 --> 26)/Cope rearrangement (26 - 23) sequence shown in Scheme 5.

  DOI：

  10.1002/(sici)1521-3765(19981102)4:11<2342::aid-chem2342>3.0.co;2-q