(+/-)-(1S*,2R*,6S*,7R*)-4-Oxatricyclo<5.2.2.0^2,6>undec-8-en-2-one | 54595-30-1

• 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: (+/-)-(1S*,2R*,6S*,7R*)-4-Oxatricyclo<5.2.2.0^2,6>undec-8-en-2-one
• 英文别名: endo-3-(hydroxymethyl)bicyclo<2.2.2>oct-5-ene-endo-2-dicarboxylic acid lactone；(+/-)-cis-endo-3-(hydroxymethyl)bicyclo<2.2.1>oct-5-ene-2-carboxylic acid lactone；cis-endo-3-oxabicyclo[2.2.2]undec-7-en-2-one；(1S,2R,6S,7R)-4-oxatricyclo[5.2.2.02,6]undec-8-en-3-one
• CAS: 54595-30-1；6715-28-2；95340-96-8；95403-17-1；151062-59-8
• 化学式: C₁₀H₁₂O₂
• 分子量: 164.204
• InChiKey: RPNZQUQOMJYWDN-UYXSQOIJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.7
• 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：

  (+/-)-(1S*,2R*,6S*,7R*)-4-Oxatricyclo<5.2.2.0^2,6>undec-8-en-2-one 生成 Z-2-carboxy-3-(hydroxymethylene)bicyclo<2.2.2>octane γ-lactone
  参考文献：
  名称：

  LOK, K. P.;JAKOVAC, I. J.;JONES, J. B., J. AMER. CHEM. SOC., 1985, 107, N 8, 2521-2526

  摘要：

  DOI：
• 作为产物：
  描述：

  meso-endo-tetrahydro-4,7-ethanoisobenzofuran-1,3-dione 在 lithium aluminium tetrahydride 、 乙醇 、 S-1,1'-联-2-萘酚 作用下， 以 四氢呋喃 为溶剂， 反应 5.0h， 以72%的产率得到(+/-)-(1S*,2R*,6S*,7R*)-4-Oxatricyclo<5.2.2.0^2,6>undec-8-en-2-one
  参考文献：
  名称：

  Enantioselective Reduction of meso-Cyclic-1,2-dicarboxylic Anhydrides and 1,2-Dicarboximides: Asymmetric Synthesis of Bicyclic Lactones and Hydroxylactams.

  摘要：

  手性双环内酯（3、8、9）和双环羟基内酰胺（10-13）是通过对meso-环状-1,2-二羧酸酐（1、4）和meso-环状-1,2-二羧酰胺（2）进行具有高对映选择性的还原反应，使用锂铝氢化物（LiAlH4）-醇（ROH）-（R）或（S）-1,1'-双-2-萘醇复合物[(R)或(S)-BINAL-H(ROH)]合成的。对羟基内酰胺（10-13）进行三乙基硅烷（Et3SiH）和三氟乙酸（CF3CO2H）的处理，得到了手性双环内酰胺（14、15），产率为定量。在高光学纯度下，用铈(IV)铵硝酸盐（CAN）顺利去除内酰胺（14、15）中的N-4-甲氧基苯基基团，得到相应的N-不取代内酰胺（16、17）。

  DOI：

  10.1248/cpb.42.9

文献信息

• Enantioselective Reduction of meso-Cyclic-1,2-dicarboxylic Anhydrides and 1,2-Dicarboximides: Asymmetric Synthesis of Bicyclic Lactones and Hydroxylactams.
  作者：Kenji MATSUKI、Hirozumi INOUE、Akihiko ISHIDA、Mikio TAKEDA、Masako NAKAGAWA、Tohru HINO

  DOI：10.1248/cpb.42.9

  日期：——

  Chiral bicyclic lactones (3, 8, 9) and bicyclic hydroxylactams (10-13) were synthesized by highly enantioselective reduction of meso-cyclic-1, 2-dicarboxylic anhydrides (1, 4) and meso-cyclic-1, 2-dicarboximides (2) with lithium aluminum hydride (LiAlH4)-alcohol(ROH)-(R)- or (S)-1, 1'-bi-2-naphthol complex [(R)- or (S)-BINAL-H(ROH)]. Treatment of the hydroxylactams (10-13) with triethylsilane (Et3SiH) and trifluoroacetic acid (CF3CO2H) gave chiral bicyclic lactams (14, 15) in quantitative yields. Removal of the N-4-methoxyphenyl group of the lactams (14, 15) with cerium(IV) ammonium nitrate (CAN) proceeded smoothly to give the corresponding N-unsubstituted lactams (16, 17) in high optical purity.

  手性双环内酯（3、8、9）和双环羟基内酰胺（10-13）是通过对meso-环状-1,2-二羧酸酐（1、4）和meso-环状-1,2-二羧酰胺（2）进行具有高对映选择性的还原反应，使用锂铝氢化物（LiAlH4）-醇（ROH）-（R）或（S）-1,1'-双-2-萘醇复合物[(R)或(S)-BINAL-H(ROH)]合成的。对羟基内酰胺（10-13）进行三乙基硅烷（Et3SiH）和三氟乙酸（CF3CO2H）的处理，得到了手性双环内酰胺（14、15），产率为定量。在高光学纯度下，用铈(IV)铵硝酸盐（CAN）顺利去除内酰胺（14、15）中的N-4-甲氧基苯基基团，得到相应的N-不取代内酰胺（16、17）。
• Microbial alcohol dehydrogenase screening for enantiopure lactone synthesis: Down-stream process from microtiter plate to bench bioreactor
  作者：F. Boratyński、J. Pannek、P. Walczak、A. Janik-Polanowicz、E. Huszcza、E. Szczepańska、E. Martinez-Rojas、T. Olejniczak

  DOI：10.1016/j.procbio.2014.06.019

  日期：2014.10

  One-pot conversion with whole cells of bacteria was performed for biooxidation of meso monocyclic (3a-b) and bicyclic diols (3c-e) into corresponding chiral lactones of bicyclo[4.3.0]nonane structure (2a-b) as well as exo- and endo-bridged lactones with the structure of [2.2.1] (3c-d) and [2.2.2] (3e). Micrococcus sp. DSM 30771 was selected as biocatalyst with significant alcohol dehydrogenase activity. Among tested strains, microbial oxidation of meso diols 3a-e catalyzed by Micrococcus sp. afforded enantiomerically pure ((+)-(2S,3R)-2c (ee = 99%), (+)-(2S,3R)-2e (ee = 99%)) or enriched ((+)-(1S,5R)-2a (ee = 90%), (-)-(1S,5R)-2b (ee = 86%), (+)-(2S,3R)-2d (ee = 80%)) lactone moieties. Comparative study with respect to microbial cultivation as well as biooxidation was undertaken to verify agreement of secondary metabolite biosynthesis in different scales: from MTP (4 mL), across shake flask (100 mL) till bioreactor (4 L). The results from biotransformations showed quite similar dependence in oxidation of all substrates 3a-e in MTP and flasks as well, thereby confirmed the validity and reasonable approach of using MTP for preliminary studies. (C) 2014 Elsevier Ltd. All rights reserved.
• Prodrugs based on masked lactones. Cyclization of .gamma.-hydroxy amides
  作者：C. David Johnson、Simon Lane、Philip N. Edwards、Peter J. Taylor

  DOI：10.1021/jo00256a040

  日期：1988.10
• Enzymes in organic synthesis. 34. Preparations of enantiomerically pure exo- and endo-bridged bicyclic [2.2.1] and [2.2.2] chiral lactones via stereospecific horse liver alcohol dehydrogenase catalyzed oxidations of meso diols
  作者：Kar P. Lok、Ignac J. Jakovac、J. Bryan Jones

  DOI：10.1021/ja00294a052

  日期：1985.4
• Enzymatic resolution of norbor(NE)nylmethanols in organic media and an application to the synthesis of (+)- and (−)-endo-Norbornene lactone.
  作者：A.J.M. Janssen、A.J.H. Klunder、B. Zwanenburg

  DOI：10.1016/s0040-4020(01)80984-4

  日期：1991.7

  The enzymatic resolution of some norbornene carboxylic acids, norbornenylmethanols and -methylamines was evaluated. The kinetic resolution of norbornyl- and norbornenylmethanols by Porcine Pancreatic Lipase (PPL)-catalyzed transesterification in methyl acetate as the solvent leads to corresponding acetates and remaining methanols both of high enantiomeric purity. A useful application is the synthesis of both enantiomers of endo-norbornene lactone 8n via transesterification of iodolactone 18. The influence of structural variations on the efficiency of the PPL-catalyzed resolution of lactone methanols 21, 23, 25 and 28, at the optimal reaction conditions established for iodolactone 18, was investigated.