cis-(1S,2R)-3-Propylcyclohexa-3,5-diene-1,2-diol

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: cis-(1S,2R)-3-Propylcyclohexa-3,5-diene-1,2-diol
• 英文别名: (1S,2R)-3-propylcyclohexa-3,5-diene-1,2-diol
• 化学式: C₉H₁₄O₂
• 分子量: 154.209
• InChiKey: NAIIGHMTELUNFI-DTWKUNHWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  cis-(1S,2R)-3-Propylcyclohexa-3,5-diene-1,2-diol 在 对甲苯磺酸 作用下， 以 丙酮 、 甲苯 为溶剂， 生成 (1S,3S,4R,7S,8S)-ethyl 7,8-isopropylidenedioxy-1-propyl-2-oxabicycle[2.2.2]-5-octen-3-carboxylate
  参考文献：
  名称：

  Aza and oxo Diels–Alder reactions using cis-cyclohexadienediols of microbial origin: chemoenzymatic preparation of synthetically valuable heterocyclic scaffolds

  摘要：

  Aza and oxo Diels-Alder reactions using enantiopure cis-cyclohexadienediols were studied. These dienediols were obtained from the biotransformation of monosubstituted arenes using bacterial dioxygenases (toluene and benzoate dioxygenases). Ethyl glyoxylate and its N-tosyl imine were used as dienophiles to afford the corresponding hetero Diels-Alder bicyclic adducts with excellent regio- and stereoselectivities. Quantum chemical calculations at the B3LYP/6-31+G(d,p) level of theory were performed to rationalize the observed selectivities especially the stereochemical aspects of the cycloadditions. The synthetic importance of these adducts is highlighted for the preparation of enantiopure 2,2,3,4,5,6-hexasubstituted piperidine and tetrahydropyran from toluene. (c) 2015 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2015.10.015
• 作为产物：
  描述：

  正丙基苯 在 Pseudomonas putida UV₄ 、 氧气 作用下， 以15%的产率得到cis-(1S,2R)-3-Propylcyclohexa-3,5-diene-1,2-diol
  参考文献：
  名称：

  对映选择性甲苯双加氧酶催化单取代苯的二羟基和三羟基化

  摘要：

  使用甲苯二加氧酶（假单胞菌中存在的生物催化剂）对一系列单取代的烷基苯底物1A-1G进行生物转化期间，发生不对称的顺式-二羟基化反应生成二醇2A-2G和顺序的苄基单羟基化-顺式二羟基化反应生成三醇4A-4G（三羟基化反应）。putida UV4。R和S苄醇对映异构体3B-3D，3B'-3D'的双加氧酶催化的顺二羟基化反应得到相应的对映纯三醇4B-4D，4B'-4D'。底物1J–1L的生物转化产生顺式二醇2J–2L和次要的三醇代谢物4A。假定苯甲醇3J-3L为不稳定的中间体，通过苯甲醛5和苯甲醇3A中间体产生三醇4A。顺含有大体积基团（单取代的苄基片二羟基化1H，1I）或1,4-二烷基-取代的苯底物（图10A-10C），获得相应的顺式-dihydrodiol代谢物（2H，2I，11A-11C））。根据NMR和CD光谱，将顺式二醇2A-2L，11A-11C和三醇4A-4F，4B'-4D'立体化学分配为1

  DOI：

  10.1039/b000753f

文献信息

• Enantioselective toluene dioxygenase catalysed di- and tri-hydroxylation of monosubstituted benzenes
  作者：Derek R. Boyd、Narain D. Sharma、Nigel I. Bowers、John Duffy、John S. Harrison、Howard Dalton

  DOI：10.1039/b000753f

  日期：——

  Asymmetric cis-dihydroxylation to yield diols 2A–2G and sequential benzylic monohydroxylation–cis-dihydroxylation to yield triols 4A–4G (trihydroxylation), occurred during biotransformation of a series of monosubstituted alkylbenzene substrates 1A–1G using toluene dioxygenase, a biocatalyst present in Pseudomonas putida UV4. Dioxygenase-catalysed cis-dihydroxylation of the R and S benzylic alcohol

  使用甲苯二加氧酶（假单胞菌中存在的生物催化剂）对一系列单取代的烷基苯底物1A-1G进行生物转化期间，发生不对称的顺式-二羟基化反应生成二醇2A-2G和顺序的苄基单羟基化-顺式二羟基化反应生成三醇4A-4G（三羟基化反应）。putida UV4。R和S苄醇对映异构体3B-3D，3B'-3D'的双加氧酶催化的顺二羟基化反应得到相应的对映纯三醇4B-4D，4B'-4D'。底物1J–1L的生物转化产生顺式二醇2J–2L和次要的三醇代谢物4A。假定苯甲醇3J-3L为不稳定的中间体，通过苯甲醛5和苯甲醇3A中间体产生三醇4A。顺含有大体积基团（单取代的苄基片二羟基化1H，1I）或1,4-二烷基-取代的苯底物（图10A-10C），获得相应的顺式-dihydrodiol代谢物（2H，2I，11A-11C））。根据NMR和CD光谱，将顺式二醇2A-2L，11A-11C和三醇4A-4F，4B'-4D'立体化学分配为1
• Site-Directed Mutagenesis Studies on the Toluene Dioxygenase Enzymatic System: Role of Phenylalanine 366, Threonine 365 and Isoleucine 324 in the Chemo-, Regio-, and Stereoselectivity
  作者：María Agustina Vila、Diego Umpiérrez、Nicolás Veiga、Gustavo Seoane、Ignacio Carrera、Sonia Rodríguez Giordano

  DOI：10.1002/adsc.201700444

  日期：2017.6.19

  in synthetic schemes. In this work, we developed three TDO mutants in residues phenylalanine 366, threonine 365 and isoleucine 324, with the aim to alter the chemo‐, regio‐ and stereoselectivity of the biotransformation of arenes. While no changes in the regioselectivity of the process were observed, dramatic variations in the chemo‐ and enantioselectivity were found for mutants I324F, T365N and F366 V

  甲苯双加氧酶（TDO）酶复合物已被广泛用作顺式的区域和对映选择性制备的生物催化剂环己二烯二醇，是有机合成的重要原料。但是，当计划在合成方案中使用这些二醇时，TDO和相关双加氧酶缺乏双加氧过程的区域和立体多样性。在这项工作中，我们开发了在残基苯丙氨酸366，苏氨酸365和异亮氨酸324中的三个TDO突变体，目的是改变芳烃生物转化的化学，区域和立体选择性。尽管未观察到该过程的区域选择性变化，但发现突变体I324F，T365N和F366 V的化学选择性和对映选择性发生了显着变化，具体取决于底物。
• Aza and oxo Diels–Alder reactions using cis-cyclohexadienediols of microbial origin: chemoenzymatic preparation of synthetically valuable heterocyclic scaffolds
  作者：Mariana Pazos、Sebastián Martínez、María Agustina Vila、Paola Rodríguez、Nicolás Veiga、Gustavo Seoane、Ignacio Carrera

  DOI：10.1016/j.tetasy.2015.10.015

  日期：2015.12

  Aza and oxo Diels-Alder reactions using enantiopure cis-cyclohexadienediols were studied. These dienediols were obtained from the biotransformation of monosubstituted arenes using bacterial dioxygenases (toluene and benzoate dioxygenases). Ethyl glyoxylate and its N-tosyl imine were used as dienophiles to afford the corresponding hetero Diels-Alder bicyclic adducts with excellent regio- and stereoselectivities. Quantum chemical calculations at the B3LYP/6-31+G(d,p) level of theory were performed to rationalize the observed selectivities especially the stereochemical aspects of the cycloadditions. The synthetic importance of these adducts is highlighted for the preparation of enantiopure 2,2,3,4,5,6-hexasubstituted piperidine and tetrahydropyran from toluene. (c) 2015 Elsevier Ltd. All rights reserved.