trans-4-iodo-trans-2-methyl-6-oxabicyclo<3.2.1>octan-7-one

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: trans-4-iodo-trans-2-methyl-6-oxabicyclo<3.2.1>octan-7-one
• 英文别名: (1RS,2RS,4SR,5SR)-4-iodo-2-methyl-6-oxabicyclo[3.2.1]octan-7-one；(1R,2R,4S, 5S)-4-iodo-2-methyl-6-oxabicyclo[3.2.1]octan-7-one；(1R,2R,4S,5S)-4-iodo-2-methyl-6-oxabicyclo[3.2.1]octan-7-one
• 化学式: C₈H₁₁IO₂
• 分子量: 266.079
• InChiKey: ZVHBATFZGOEACL-JWXFUTCRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  trans-4-iodo-trans-2-methyl-6-oxabicyclo<3.2.1>octan-7-one 在 偶氮二异丁腈 、 三正丁基氢锡 、 sodium ethanolate 作用下， 以 苯 为溶剂， 反应 1.0h， 生成 ethyl (1R,2R,5R)-5-hydroxy-2-methyl-1-carboxylate
  参考文献：
  名称：

  Enantioselective Synthesis of Ceralure B1, Ethyl cis-5-Iodo-trans-2-methylcyclohexane-1-carboxylate

  摘要：

  Ethyl (1R, 2R, SR)-5-iodo-2-methylcyclohexane-1-carboxylate is a potent attractant for the Mediterranean fruit fly. This compound was stereoselectively synthesized on a multigram scale in nine steps in 15% yield. Key steps of the synthesis involved an asymmetric Diels-Alder reaction, iodolactonization, stereoselective reduction of the carbonyl, and inversion of configuration with iodide. Published by Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4020(00)00219-2
• 作为产物：
  描述：

  (1S,6S)-6-methyl-3-cyclohexene-1-carboxylic acid 在 碘 、 碳酸氢钠 、 potassium iodide 作用下， 以 二氯甲烷 、 水 为溶剂， 反应 0.5h， 生成 trans-4-iodo-trans-2-methyl-6-oxabicyclo<3.2.1>octan-7-one
  参考文献：
  名称：

  通过Pd 2+促进的环烯基化反应全合成（±）-组酯

  摘要：

  从反式-2-甲基-4-环己烯羧酸（9）开始，已经完成了线性三喹烷倍半萜烯（±）-杂多烯（1）的全合成。序列的关键步骤采用酸催化的分子内共轭物加成（7→6a）和Pd 2+促进的高度立体控制的环化（5→4）。有趣的是，某些合成中间体表现出细胞毒性。

  DOI：

  10.1016/s0040-4020(01)81806-8

文献信息

• Total Synthesis of (±)-Hirsutene via Pd2+-Promoted Cycloalkenylation Reaction
  作者：Masahiro Toyota、Youichi Nishikawa、Kayoko Motoki、Naomi Yoshida、Keiichiro Fukumoto

  DOI：10.1016/s0040-4020(01)81806-8

  日期：1993.1

  Beginning with trans-2-methyl-4-cyclohexenecarboxylic acid (9), a total synthesis of linear triquinane sesquiterpene (±)-hirsutene (1) has been accomplished. An acid catalyzed intramolecular conjugate addition (7→6a) and a Pd2+-promoted highly stereocontrolled cyclization (5→4) were utilized for the key step of the sequence. Interestingly, some synthetic intermediates exhibited cytotoxicity.

  从反式-2-甲基-4-环己烯羧酸（9）开始，已经完成了线性三喹烷倍半萜烯（±）-杂多烯（1）的全合成。序列的关键步骤采用酸催化的分子内共轭物加成（7→6a）和Pd 2+促进的高度立体控制的环化（5→4）。有趣的是，某些合成中间体表现出细胞毒性。
• Regioselective synthesis of ceralure B1 and A, ethyl cis-(and trans-) 5-iodo-trans-2-methylcyclohexane-1-carboxylate
  作者：James W. Avery、Roy T. Cunningham、Rolland M. Waters

  DOI：10.1016/s0040-4039(00)78536-4

  日期：1994.12

  Reaction of trans-2-methyl-6-oxabicyclo[3.2.1]octan-7-one with trimethylsilyl iodide, generated in situ, followed by refluxing with ethanol gives regioselectively ethyl cis-(and trans-) 5-iodo-2-methylcyclohexane-1-carboxylate, a persistent attractant for male Mediterranean fruit flies.

  的反应反式-2-甲基-6-氧杂二环[3.2.1]辛-7-酮与三甲基碘硅烷，在原位产生的，随后用乙醇回流给出区域选择性乙基顺式- （和反式- ）5-碘-2-甲基环己烷-1-甲酸甲酯，是地中海雄性果蝇的持久引诱剂。
• Attractant for the mediterranean fruit fly, the method of preparation and method of use
  申请人：The United States of America as represented by the Secretary of Agriculture

  公开号：US06375943B1

  公开（公告）日：2002-04-23

  A method of attracting the Mediterranean fruit fly by subjecting the Mediterranean fruit fly to an attractant, wherein the attractant is ethyl (1R,2R,5R)-5-iodo-2-methylcyclohexane-1-carboxylate in an enantomeric excess of at least 70% and a regio- and diastereochemical purity of >5:1. The compound ethyl (1R,2R,5R)-5-iodo-2-methylcyclohexane-1-carboxylate, in an enantomeric excess of at least 70% and a regio- and diastereochemical purity of >5:1, may be stereoselectively synthesized on a multigram scale in 15% yield by reacting ethyl (1R,2R,5S)-5-hydroxy-2-methyl-1-carboxylate with Ph3P-imidazole-I2 (or Ph3P-2,6-lutidine-I2) in a carbon tetrachloride/methlylene chloride mixture. The 1R,2R,5R enantiomer is significantly more attractive than its enantiomeric counterpart (1S,2S,5S), or either of the commercial products trimedlure or ceralure, each a mixture of 16 regio and stereoisomers.

  通过将地中海果蝇暴露于一种引诱剂中来吸引地中海果蝇的方法，其中引诱剂是乙基(1R,2R,5R)-5-碘-2-甲基环己烷-1-羧酸乙酯，其对映体过量至少为70%，区域和立体化学纯度大于5:1。乙基(1R,2R,5R)-5-碘-2-甲基环己烷-1-羧酸乙酯化合物，在对映体过量至少为70%和区域和立体化学纯度大于5:1的情况下，可通过将乙基(1R,2R,5S)-5-羟基-2-甲基-1-羧酸乙酯与Ph3P-咪唑-碘（或Ph3P-2,6-吖啶-碘）在四氯化碳/甲基氯仿混合物中反应，在15%的产率下立体选择性地合成多克级规模的1R,2R,5R对映体。1R,2R,5R对映体比其对映体对应物（1S,2S,5S）或商业产品trimedlure或ceralure更具吸引力，trimedlure或ceralure是16个区域和立体异构体的混合物。
• Method for the synthesis of ceralure B1
  申请人：The United States of America as represented by the Secretary of Agriculture

  公开号：US06777573B1

  公开（公告）日：2004-08-17

  A method has been developed for the preparation of ceralure B1, a potent attractant for the Mediterranean fruit fly. The method utilizes trans-siglure acid as starting material to produce iodolactone which is subsequently reduced to lactone. The lactone is converted to a mixture of epimers ceralure A acid and ceralure B1 acid. The ceralure A acid is recyclized to lactone, leaving epimer ceralure B1 acid intact. Following separation from lactone, the ceralure B1 acid is esterified to produce ceralure B1 of about 92-94% purity. The overall yield is about 58-65%, a significant improvement over currently known methods which result in yields of about 30-33%.

  已开发出一种制备地中海果蝇强效引诱剂Ceralure B1的方法。该方法利用顺式半萜酸作为起始物质，制备碘内酯，随后还原为内酯。内酯转化为混合外消旋体Ceralure A酸和Ceralure B1酸。Ceralure A酸回收重环化为内酯，使外消旋体Ceralure B1酸保持不变。从内酯中分离后，Ceralure B1酸酯化，制备出约92-94％纯度的Ceralure B1。总收率约为58-65％，明显优于目前已知的方法，其产率约为30-33％。
• US6375943B1
  申请人：——

  公开号：US6375943B1

  公开（公告）日：2002-04-23