(4R,5S,7S,8R,9S,10R,11R)-7,8-diacetyloxy-9-mesyloxy-1-oxolongipin-2-ene | 161941-47-5

• 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: (4R,5S,7S,8R,9S,10R,11R)-7,8-diacetyloxy-9-mesyloxy-1-oxolongipin-2-ene
• CAS: 161941-47-5
• 化学式: C₂₀H₂₈O₈S
• 分子量: 428.504
• InChiKey: VHLKAOZIYBCDMU-OOMXFDOZSA-N

反应信息

• 作为反应物：
  描述：

  (4R,5S,7S,8R,9S,10R,11R)-7,8-diacetyloxy-9-mesyloxy-1-oxolongipin-2-ene 在 氢氧化钾 、 水 作用下， 以 1,4-二氧六环 、 甲醇 为溶剂， 反应 2.33h， 生成 (5S)-4,5-dihydroxy-2,6,6,9-tetramethylpentacyclo[5.4.0.02,10.03,9.04,8]undecan-11-one
  参考文献：
  名称：

  Generation of the new quirogane skeleton by a vinylogous retro-Michael type rearrangement of longipinene derivatives

  摘要：

  A new tricyclic hydrocarbon skeleton, named quirogane, was prepared by a vinylogous retro-Michael type molecular rearrangement of (4R,5S,7R,8R,9S,10R,11R)-7,8-diacetyloxy-9-mesyloxy-1-oxolongipin-2-ene (5). A remarkable difference in chemical behavior as compared to the corresponding 2,3-dihydroderivative of 5 is explained in terms of the stability of anionic intermediates, which were evaluated by AMI calculations. The structure of the quirogane skeleton was confirmed by single crystal X-ray diffraction analysis of quirogadiene 6. A [2+2] photochemical cyclization of 6 afforded the highly strained pentacyclic sesquiterpenoid (10). (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(01)00718-9
• 作为产物：
  描述：

  甲基磺酰氯 、 Acetic acid (1R,4aR,5R,6S,7S,8S,9aS)-8-acetoxy-6-hydroxy-4,5,9,9-tetramethyl-2-oxo-2,4a,5,6,7,8,9,9a-octahydro-1H-1,5-cyclo-benzocyclohepten-7-yl ester 在 吡啶 作用下， 反应 24.0h， 以57%的产率得到(4R,5S,7S,8R,9S,10R,11R)-7,8-diacetyloxy-9-mesyloxy-1-oxolongipin-2-ene
  参考文献：
  名称：

  Generation of the new quirogane skeleton by a vinylogous retro-Michael type rearrangement of longipinene derivatives

  摘要：

  A new tricyclic hydrocarbon skeleton, named quirogane, was prepared by a vinylogous retro-Michael type molecular rearrangement of (4R,5S,7R,8R,9S,10R,11R)-7,8-diacetyloxy-9-mesyloxy-1-oxolongipin-2-ene (5). A remarkable difference in chemical behavior as compared to the corresponding 2,3-dihydroderivative of 5 is explained in terms of the stability of anionic intermediates, which were evaluated by AMI calculations. The structure of the quirogane skeleton was confirmed by single crystal X-ray diffraction analysis of quirogadiene 6. A [2+2] photochemical cyclization of 6 afforded the highly strained pentacyclic sesquiterpenoid (10). (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(01)00718-9