(3aR,7aS)-2,2,4-trimethyl-3a,7a-dihydro-1,3-benzodioxole | 114763-30-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (3aR,7aS)-2,2,4-trimethyl-3a,7a-dihydro-1,3-benzodioxole
• 英文别名: (1S,2R)-1,2-O-isopropylidene-3-methylcyclohexa-3,5-diene-1,2-diol；(2R,3S)-1-methyl-2,3-(isopropylidenedioxy)cyclohexa-4,6-diene；(3aR,7aS)-3a,7a-dihydro-2,2,4-trimethylbenzo[1,3]dioxole；(3aR,7aS)-3a,7a-dihydro-2,2,4-trimethyl-1,3-benzodioxole
• CAS: 114763-30-3
• 化学式: C₁₀H₁₄O₂
• 分子量: 166.22
• InChiKey: RBYIHMVPMDCKTL-DTWKUNHWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (3aR,7aS)-2,2,4-trimethyl-3a,7a-dihydro-1,3-benzodioxole 在 亚磷酸三苯酯 、 aluminum oxide 、 sodium periodate 、 四氧化锇 、 phosphate buffer 、 臭氧 、 氢化铝 、 mercury dichloride 作用下， 以 1,4-二氧六环 、 甲醇 、 乙二醇二甲醚 、 乙醚 、 二氯甲烷 、 水 为溶剂， 反应 22.75h， 生成 (+/-)-2,2-dimethyl-3αβ,6αβ-dihydro-4H-cyclopenta-1,3-dioxol-4-one
  参考文献：
  名称：

  通过芳烃的微生物氧化进行对映选择性合成。1.萜类和前列腺素合成子的高效制备

  摘要：

  Le cis-tolediol est obtenu par biodegradation du犰狋犰狳假单胞菌, souche 39D, et est un substrat pour la synthese de prostaglandine

  DOI：

  10.1021/ja00222a035
• 作为产物：
  描述：

  (3aS,7aS)-2,2-dimethyl-7,7a-dihydrobenzo[d][1,3]dioxol-4-(3aH)-one 在 吡啶 、 氯化亚砜 、 lithium carbonate 、 lithium chloride 作用下， 以 乙醚 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 生成 (3aR,7aS)-2,2,4-trimethyl-3a,7a-dihydro-1,3-benzodioxole
  参考文献：
  名称：

  Chemical synthesis of optically active cis-cyclohexa-3,5-diene-1,2-diols and their 5-2H-derivatives

  摘要：

  A variety of optically active 3-substituted cis-cyclohexane-3,5-dien-1,2-diol acetonides were readily prepared from chiral 5-(tert-butyldimethylsilyloxy)-2-cyclohexenone through a seven-step reaction in good overall yield. The synthesis also allowed preparation of the acetonide having an H-2-atom at the 5-position. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(01)01014-0

文献信息

• The Chemoenzymatic Total Synthesis of Phellodonic Acid, a Biologically Active and Highly Functionalized Hirsutane Derivative Isolated from the Tasmanian Fungus Phellodon melaleucus
  作者：Tristan A. Reekie、Kerrie A. B. Austin、Martin G. Banwell、Anthony C. Willis

  DOI：10.1071/ch07403

  日期：——

  A total synthesis of the title natural product, 1, has been achieved using the cis-1,2-dihydrocatechol 7 as starting material. Compound 7 is readily obtained in large quantity and in an enantiomerically pure form through the whole-cell biotransformation of toluene using the genetically engineered microorganism E. coli JM109 (pDTG601) that overexpresses the enzyme toluene dioxygenase (TDO). Three key chemical steps were employed in the synthesis, the first of which was the microwave-promoted Diels–Alder cycloaddition reaction between diene 8 and cyclopent-1-en-2-one to give adduct 9. The second key step was the photochemically promoted oxa-di-π-methane rearrangement of the bicyclo[2.2.2]octenone derivative 15 of 9 to give the epimers 16 and 17, and the third key step was the reductive cleavage of the last pair of compounds so as to afford the linear triquinane 19. Elaboration of compound 19 to target 1 followed established procedures. Single-crystal X-ray analyses were carried out on compounds 11 and 19.

  以顺式-1,2-二氢邻苯二酚 7 为起始原料，实现了标题天然产物 1 的全合成。利用基因工程微生物大肠杆菌 JM109 (pDTG601)过量表达甲苯二氧 化酶（TDO），通过甲苯的全细胞生物转化，很容易获得大量对映体纯的化合物 7。合成过程中采用了三个关键化学步骤，第一个步骤是二烯 8 与环戊-1-烯-2-酮发生微波促进的 Diels-Alder 环加成反应，生成加合物 9。第二个关键步骤是光化学促进 9 的双环[2.2.2]辛烯酮衍生物 15 的氧杂-二-π-甲烷重排反应，得到外延物 16 和 17，第三个关键步骤是最后一对化合物的还原裂解，得到线性三喹啉 19。按照既定程序将化合物 19 制成目标化合物 1。对化合物 11 和 19 进行了单晶 X 射线分析。
• Reaction of diphenylketene with some cyclohexa-3,5-diene-1,2-cis-diol derivatives: conversion of chlorobenzene into optically active 2-oxabicyclo[2.2.2]octen-3-one
  作者：Carlos A. Pittol、Stanley M. Roberts、Peter W. Sutton、Julian O. Williams

  DOI：10.1039/c39940000803

  日期：——

  The dienes 11–15 react with diphenylketene to give mixtures of the corresponding [2 + 2]-adducts 16–20 and [4 + 2]-adducts 21–25: the isomers 19/24 were converted into the optically active lactone 26 in two steps.

  二烯11-15与二苯基乙烯酮反应得到的混合物的相应的[2 + 2] -adducts 16-20和[4 + 2] -adducts 21-25：异构体19/24转化成光学活性内酯26在两步。
• Chemoenzymatic synthesis of the trans-dihydrodiol isomers of monosubstituted benzenes viaanti-benzene dioxides
  作者：Derek R. Boyd、Narain D. Sharma、Nuria M. Llamas、Colin R. O'Dowd、Christopher C. R. Allen

  DOI：10.1039/b603928f

  日期：——

  dioxygenase-catalysed cis-dihydroxylation of monosubstituted benzene substrates, have been used as synthetic precursors of the corresponding trans-3,4-dihydrodiols. The six-step chemoenzymatic route from cis-dihydrodiol precursors, involving acetonide, tetraol, dibromodiacetate and diepoxide intermediates, and substitution of vinyl bromide and iodide atoms, has been used in the synthesis of ten trans-dihydrododiol derivatives

  可从单取代苯底物的双加氧酶催化的顺式-二羟基化获得的对映体纯的顺式2，3-二氢二醇已用作相应的反式3，4-二氢二醇的合成前体。顺式-二氢二醇前体的六步化学酶法路线涉及乙醛，四醇，二溴二乙酸酯和二环氧化合物中间体，以及乙烯基溴和碘原子的取代，已用于合成十种取代苯的反式-二氢二二醇衍生物。该方法在甲苯的反式1,2-和3,4-二氢二醇衍生物的两种对映异构体的合成中的使用已经证明了该方法的普遍适用性。
• General Method for the Synthesis of (−)-Conduritol C and Analogs from Chiral Cyclohexadienediol Scaffolds
  作者：Gaurao Tibhe、Mario Macías、Valeria Schapiro、Leopoldo Suescun、Enrique Pandolfi

  DOI：10.3390/molecules23071653

  日期：——

  permitted the absolute configuration of the carbon bearing the hydroxyl groups at the target molecules to be established. All three conduritols and two intermediates were crystallized, and their structures were confirmed by X-ray diffraction. The three conduritols and intermediates were isostructural. The versatility of our methodology is noteworthy to expand the preparation of conduritol C analogs starting

  描述了一种利用单取代苯的对映选择性生物催化过程合成 conduritol C 类似物的有效和简便的通用方法。目标分子 (-)-conduritol C、(-)-bromo-conduritol C 和 (-)-methyl-conduritol C 的绝对立体化学模式是通过化学酶法实现的。源自芳烃生物转化的同手性环己二烯-顺-1,2-二醇的立体化学和非分离的乙烯基环氧化物衍生物的对映选择性开环允许在目标分子上建立带有羟基的碳的绝对构型. 所有三种球状糖醇和两种中间体均已结晶，并通过 X 射线衍射证实了它们的结构。三种结构糖醇和中间体是同构的。我们方法的多功能性值得注意，可扩展从甲苯双加氧酶 (TDO) 单取代芳烃底物开始制备 conduritol C 类似物。
• Reactions of diphenylketene and methylphenylketene with some cis-cyclohexa-3,5-diene-1,2-diol derivatives
  作者：Stanley M. Roberts、Peter W. Sutton、Lorraine Wright

  DOI：10.1039/p19960001157

  日期：——

  The reaction of the dienes 1–5 with diphenylketene to give the [2 + 2]-adducts 6–10 and the [4 + 2]-adducts 11–15, respectively, has been found to occur by an ionic mechanism involving the zwitterion 16. The reactions of the dienes 2 and 3 with methylphenylketene (and also cyclohexa-1,3-diene with diphenylketene) proceed in a similar fashion. The enol ether 13 was converted into the polyoxygenated cyclohexane derivatives 33, 35 and 38.

  与二苯基酮烯反应的二烯体1-5分别生成[2 + 2]加成物6-10和[4 + 2]加成物11-15，已发现该反应通过一种离子机制进行，涉及双性离子16。二烯体2和3与甲基苯基酮烯（以及环己烯-1,3与二苯基酮烯）的反应以类似方式进行。醇醚13转化为多氧化的环己烷衍生物33、35和38。