(E)-(4S,7R,8S,9S,16S)-4,8-Dihydroxy-5,5,7,9,13-pentamethyl-16-[(E)-1-methyl-2-(2-methyl-oxazol-4-yl)-vinyl]-oxacyclohexadec-13-ene-2,6-dione | 198571-11-8

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 大环内酯类和类似物
• 英文名称: (E)-(4S,7R,8S,9S,16S)-4,8-Dihydroxy-5,5,7,9,13-pentamethyl-16-[(E)-1-methyl-2-(2-methyl-oxazol-4-yl)-vinyl]-oxacyclohexadec-13-ene-2,6-dione
• CAS: 198571-11-8
• 化学式: C₂₇H₄₁NO₆
• 分子量: 475.626
• InChiKey: QJBTYCVYJKZKMC-SKHVSTCVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  34.0
• 可旋转键数：
  2.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  109.86
• 氢给体数：
  2.0
• 氢受体数：
  7.0

反应信息

• 作为反应物：
  描述：

  (E)-(4S,7R,8S,9S,16S)-4,8-Dihydroxy-5,5,7,9,13-pentamethyl-16-[(E)-1-methyl-2-(2-methyl-oxazol-4-yl)-vinyl]-oxacyclohexadec-13-ene-2,6-dione 在 间氯过氧苯甲酸 作用下， 以 氯仿 为溶剂， 反应 3.0h， 以7%的产率得到(1R,3S,7S,10R,11S,12S,16R)-7,11-Dihydroxy-8,8,10,12,16-pentamethyl-3-[(E)-1-methyl-2-(2-methyl-oxazol-4-yl)-vinyl]-4,17-dioxa-bicyclo[14.1.0]heptadecane-5,9-dione
  参考文献：
  名称：

  Total Synthesis of Oxazole- and Cyclopropane-Containing Epothilone B Analogues by the Macrolactonization Approach

  摘要：

  AbstractIn order to probe structure‐activity relationships in the epothilone area, two series of epothilone B analogues have been designed and synthesized. The first series containing an oxazole moiety in place of a thiazole on the side chain was constructed by utilizing key intermediates 7–9 or 10, 12, and 13 (Scheme 1), whereas the second series containing an ethano group instead of the gem‐dimethyl group at position 4 was synthesized from fragments 42 and 43. A Yamaguchi‐type macrolactonization reaction was used to construct the macrocycle from a secoacid, which was assembled, in both cases, by means of a) an aldol reaction, b) an Enders alkylation, and c) a Wittig‐type reaction. This convergent strategy provided access to oxazole analogues 2,4,29–32 and 4,4‐ethano derivatives 3,40,60–63 for biological studies.

  DOI：

  10.1002/chem.19970031212
• 作为产物：
  描述：

  (E)-(S)-3-(tert-Butyl-dimethyl-silanyloxy)-4-methyl-5-(2-methyl-oxazol-4-yl)-pent-4-enal 在 咪唑 、 2,6-二甲基吡啶 、 4-二甲氨基吡啶 、 sodium chlorite 、 sodium tetrahydroborate 、 sodium dihydrogenphosphate 、 2-甲基-2-丁烯 、 草酰氯 、 pyridine-SO3 complex 、 2,4,6-三氯苯甲酰氯 、 camphor-10-sulfonic acid 、 四丁基氟化铵 、 碘 、 sodium hexamethyldisilazane 、 氟化氢吡啶 、 二甲基亚砜 、 三乙胺 、 三苯基膦 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 正己烷 、 二氯甲烷 、 乙腈 、 叔丁醇 为溶剂， 反应 71.0h， 生成 (E)-(4S,7R,8S,9S,16S)-4,8-Dihydroxy-5,5,7,9,13-pentamethyl-16-[(E)-1-methyl-2-(2-methyl-oxazol-4-yl)-vinyl]-oxacyclohexadec-13-ene-2,6-dione
  参考文献：
  名称：

  Total Synthesis of Oxazole- and Cyclopropane-Containing Epothilone B Analogues by the Macrolactonization Approach

  摘要：

  AbstractIn order to probe structure‐activity relationships in the epothilone area, two series of epothilone B analogues have been designed and synthesized. The first series containing an oxazole moiety in place of a thiazole on the side chain was constructed by utilizing key intermediates 7–9 or 10, 12, and 13 (Scheme 1), whereas the second series containing an ethano group instead of the gem‐dimethyl group at position 4 was synthesized from fragments 42 and 43. A Yamaguchi‐type macrolactonization reaction was used to construct the macrocycle from a secoacid, which was assembled, in both cases, by means of a) an aldol reaction, b) an Enders alkylation, and c) a Wittig‐type reaction. This convergent strategy provided access to oxazole analogues 2,4,29–32 and 4,4‐ethano derivatives 3,40,60–63 for biological studies.

  DOI：

  10.1002/chem.19970031212