<1(Z)>-17,18-Didehydro-7-(4,8-dimethyl-3,7-nonadienyl)-12,16-cyclo-21,22,23-trinor-1,12-secodaphnane | 138409-37-7

• 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: <1(Z)>-17,18-Didehydro-7-(4,8-dimethyl-3,7-nonadienyl)-12,16-cyclo-21,22,23-trinor-1,12-secodaphnane
• CAS: 138409-37-7
• 化学式: C₃₀H₄₇N
• 分子量: 421.71
• InChiKey: BQBIWYQYARNZHX-JXTCZURBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.99
• 重原子数：
  31.0
• 可旋转键数：
  7.0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  12.03
• 氢给体数：
  1.0
• 氢受体数：
  1.0

反应信息

• 作为产物：
  描述：

  <3α,3aβ,6α(Z),6aα,9aR^*,10S^*>-(+/-)-2,3,3a,6,6a,7,8,9-Octahydro-10-methyl-10-(4-methyl-3-pentenyl)-6-(4,8-dimethyl-3,7-nonadienyl)-3,6-methano-1H-dicyclopentapyridine 在 ammonium acetate 、 溶剂黄146 作用下， 反应 2.0h， 以90%的产率得到<1(Z)>-17,18-Didehydro-7-(4,8-dimethyl-3,7-nonadienyl)-12,16-cyclo-21,22,23-trinor-1,12-secodaphnane
  参考文献：
  名称：

  Daphniphyllum alkaloids. 12. A proposed biosynthesis of the pentacylic skeleton. proto-Daphniphylline

  摘要：

  A biosynthetic proposal for the pentacyclic skeleton of the Daphniphyllum alkaloids is put forth (Scheme I) and various ramifications are examined experimentally. proto-Daphniphylline (11), the putative product of this hypothetical biogenesis, has been prepared by a convergent synthesis that starts with amide 14, alpha,beta-unsaturated ester 15, and homogeranyl iodide (Scheme II) and employs a highly efficient tetracyclization process previously used for the synthesis of (+/-)-methyl homosecodaphniphyllate (30) (Scheme III). The structure of proto-daphniphylline was confirmed by converting it into 30. The mechanism of the first stage of the tetracyclization process was investigated with the bis-homoneryl analogues 36/37. Treatment of these aldehydes successively with ammonia and acetic acid provided tetracyclic imine 38, suggesting that the cyclization reaction is a concerted Diels-Alder reaction rather than a stepwise process. Dialdehydes 27/28 were converted into 1,2-dihydro-proto-daphniphylline (29) by a version of the tetracyclization process wherein methylamine (or glycine) is substituted for ammonia. proto-Daphniphylline has also been prepared in a one-pot, two-stage process from the acyclic dialdehydes 51 and 55. Several versions of this pentacyclization process have been worked out. In the simplest, 51 or 55 is treated successively with ammonia and hot acetic acid to afford 11 in 15 +/- 2% yield. A slightly more elaborate protocol, a three-stage process that utilizes NaOH in benzene, ammonia in DMSO, and hot acetic acid, provided 11 in 49.4% overall yield. However, the most efficient pentacyclization process discovered employs successive reactions with methylamine (or glycine) and hot acetic acid. Under these conditions, 17,18-dihydro-proto-daphniphylline (29) is produced in 65% yield. The latter process is one of the most efficient reaction cascades ever discovered; it results in the formation of five rings, four carbon-carbon bonds, two carbon-nitrogen bonds, and concludes with the selective saturation of one of the three double bonds in proto-daphniphylline!

  DOI：

  10.1021/jo00035a009