11β-phenylseleno-5,7,8αH-elema-1,3-dien-8,12-olide | 126784-59-6

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 11β-phenylseleno-5,7,8αH-elema-1,3-dien-8,12-olide
• 英文别名: (3S,3aS,5S,6S,7aR)-6-ethenyl-3,6-dimethyl-3-phenylselanyl-5-prop-1-en-2-yl-4,5,7,7a-tetrahydro-3aH-1-benzofuran-2-one
• CAS: 126784-59-6
• 化学式: C₂₁H₂₆O₂Se
• 分子量: 389.396
• InChiKey: UJTASIWQPVDZQL-NRVIEEGESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.91
• 重原子数：
  24.0
• 可旋转键数：
  4.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.48
• 拓扑面积：
  26.3
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  11β-phenylseleno-5,7,8αH-elema-1,3-dien-8,12-olide 在 吡啶 、 双氧水 作用下， 以 四氢呋喃 为溶剂， 反应 0.5h， 以88%的产率得到(5R,7R,8R,10S)-elema-1,3,11(13)-trien-8,12-olide
  参考文献：
  名称：

  The use of 4,4-disubstituted nopinones for natural-product synthesis. Synthesis of elemanoid sesquiterpenes

  摘要：

  A general and convenient synthetic route to 4,4-disubstituted nopinones 14 from (+)-nopinone (1) is developed and applied to the asymmetric synthesis of some representative elemanoid sesquiterpenes. Phenylsulfenylation of 1 provided sulfide 6 in high yield. A convenient transformation of 6 to 3-(phenylsulfonyl)-4,4-disubstituted-nopinones 13 was accomplished by (i) m-CPBA oxidation of a sulfide compound followed by the Pummerer rearrangement and (ii) the conjugate addition of carbon nucleophiles to the resulting enones, 6 --> 8 --> 9 and 9 --> 10,11 --> 13. Subsequent reductive desulfurization of the adducts 13 provided 14 in good overall yield from 1. Bicyclic ketones 14 are envisioned as promising intermediates for natural product synthesis. As examples, syntheses of two elemanoid sesquiterpenes, beta-elemenone (16) and eleman-8-beta,12-olide (17) in optically active form from (1R,4S,5S)-4,6,6-trimethyl-4-vinylbicyclo[3.1.1]heptan-2-one (14a) were carried out.

  DOI：

  10.1021/jo00025a023
• 作为产物：
  描述：

  (1R,3RS,4S,5R)-4,6,6-Trimethyl-3-(phenylsulfonyl)-4-vinylbicyclo<3.1.1>heptan-2-one 在 六甲基磷酰三胺 、 lithium tri(t-butoxy)aluminum hydride 、 三氟化硼乙醚 、 zinc diacetate 、 氨 、 甲基锂 、 lithium 、 对甲苯磺酸 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 75.33h， 生成 11β-phenylseleno-5,7,8αH-elema-1,3-dien-8,12-olide
  参考文献：
  名称：

  The use of 4,4-disubstituted nopinones for natural-product synthesis. Synthesis of elemanoid sesquiterpenes

  摘要：

  A general and convenient synthetic route to 4,4-disubstituted nopinones 14 from (+)-nopinone (1) is developed and applied to the asymmetric synthesis of some representative elemanoid sesquiterpenes. Phenylsulfenylation of 1 provided sulfide 6 in high yield. A convenient transformation of 6 to 3-(phenylsulfonyl)-4,4-disubstituted-nopinones 13 was accomplished by (i) m-CPBA oxidation of a sulfide compound followed by the Pummerer rearrangement and (ii) the conjugate addition of carbon nucleophiles to the resulting enones, 6 --> 8 --> 9 and 9 --> 10,11 --> 13. Subsequent reductive desulfurization of the adducts 13 provided 14 in good overall yield from 1. Bicyclic ketones 14 are envisioned as promising intermediates for natural product synthesis. As examples, syntheses of two elemanoid sesquiterpenes, beta-elemenone (16) and eleman-8-beta,12-olide (17) in optically active form from (1R,4S,5S)-4,6,6-trimethyl-4-vinylbicyclo[3.1.1]heptan-2-one (14a) were carried out.

  DOI：

  10.1021/jo00025a023

文献信息

• Synthesis of various natural 8,12-elemanolides from artemisin
  作者：Gonzalo Blay、Isabel Fernández、Begoña García、José R. Pedro

  DOI：10.1016/s0040-4020(01)89119-5

  日期：1989.1
• FRIEDRICH, DIRK;BOHLMANN, FERDINAND, TETRAHEDRON, 44,(1988) N 5, 1369-1392
  作者：FRIEDRICH, DIRK、BOHLMANN, FERDINAND

  DOI：——

  日期：——