(1S,2S,3R)-4-Bromo-2,3-O-isopropylidenecyclohex-4-ene-1,2,3-triol | 139432-90-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1S,2S,3R)-4-Bromo-2,3-O-isopropylidenecyclohex-4-ene-1,2,3-triol
• 英文别名: (1S,2S,3R)-4-bromo-2,3-isopropylidenecyclohex-5-ene-1-ol；(3aS,4R,7aS)-7-bromo-2,2-dimethyl-3a,4,5,7a-tetrahydro-1,3-benzodioxol-4-ol
• CAS: 139432-90-9
• 化学式: C₉H₁₃BrO₃
• 分子量: 249.104
• InChiKey: LQSYFGBRSWVOAN-PRJMDXOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  13
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  38.7
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (1S,2S,3R)-4-Bromo-2,3-O-isopropylidenecyclohex-4-ene-1,2,3-triol 在 咪唑 、 偶氮二异丁腈 、 三正丁基氢锡 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 生成 (1R,2R,3R)-1-O-[dimethyl(1,1,2-trimethylpropyl)silyl]-2,3-O-isopropylidenecyclohex-4-ene-1,2,3-triol
  参考文献：
  名称：

  Chemoenzymatic preparation of (6R)-5,6-dihydro-2H-pyran-2-one: a ubiquitous structural motif of biologically active lactones

  摘要：

  A chemoenzymatic synthesis of an enantiopure 6-substituted 5,6-dihydro-2H-pyran-2-one using bromobenzene as a starting material is presented. This important structural motif is found in a large number of chiral lactones that present a wide range of biological activities. The key features of the preparation include enzymatic dioxygenation of bromobenzene using Escherichia coli JM109 (pDTG601), microwave-assisted acyloin cleavage, and tin mediated lactonization. The stereochemical assignment for the alcohol was confirmed by NMR analysis of Moshers derivatives. (C) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2013.10.005
• 作为产物：
  描述：

  (3aS,7aS)-4-bromo-2,2-dimethyl-3a,7a-dihydro-1,3-benzodioxole 在 lithium aluminium tetrahydride 、 间氯过氧苯甲酸 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 生成 (1S,2S,3R)-4-Bromo-2,3-O-isopropylidenecyclohex-4-ene-1,2,3-triol
  参考文献：
  名称：

  Chemoenzymatic preparation of (6R)-5,6-dihydro-2H-pyran-2-one: a ubiquitous structural motif of biologically active lactones

  摘要：

  A chemoenzymatic synthesis of an enantiopure 6-substituted 5,6-dihydro-2H-pyran-2-one using bromobenzene as a starting material is presented. This important structural motif is found in a large number of chiral lactones that present a wide range of biological activities. The key features of the preparation include enzymatic dioxygenation of bromobenzene using Escherichia coli JM109 (pDTG601), microwave-assisted acyloin cleavage, and tin mediated lactonization. The stereochemical assignment for the alcohol was confirmed by NMR analysis of Moshers derivatives. (C) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2013.10.005

文献信息

• Toluene-Dioxygenase-Mediated cis-Dihydroxylation of Aromatics in Enantioselective Synthesis. Iterative Glycoconjugate CouplingStrategy and Combinatorial Design for the Synthesis of Oligomers of nor-Saccharides,Inositols and Pseudosugars with Interesting Molecular Properties
  作者：Tomas Hudlicky、Khalil A. Abboud、David A. Entwistle、Rulin Fan、Rakesh Maurya、Andrew J. Thorpe、Joel Bolonick、Brian Myers

  DOI：10.1055/s-1996-4440

  日期：1996.7

  The authors wish to dedicate this article to the memory of Professor WolfgangOppolzer, who passed away on March 15, 1996. Professor Oppolzer’s contributionsto the art and craft of organic synthesis and his energetic career were cutshort by this untimely tragedy, which has left a serious void in the syntheticcommunity. His intellectual capacity and his style of problem solving servedas an example and inspiration to many of us. Tomas Hudlicky was a postdoctoralfellow in Geneva during the early years of Professor Oppolzer’s academiccareer. He credits much of this success as an independent investigator tothe mentorship he received in 1977-78 from Professor Oppolzer; he is deeplyaffected by the loss of one of the great practitioners. Vinyl epoxides 18 Caret and 31 and vinylaziridines 24and 25 derived from chloro- or bromocyclohexadiene-cis-diols 9 have been condensed with protected cyclitols 19, 37, and 46 in an iterative manner to generate dimeric,trimeric and tetrameric conduritol or aminocyclitol conjugates which on furtherfunctionalization of the olefins and deprotection yielded inositol conjugates 22, 53, and 59 and aminocyclito conjugates 30, 36 and 45. Iodocyclohexadiene-cis-diol 71 and methyl shikimate 82 were used as synthons for thesynthesis of pseudo-β-D-glucopyranose 85 and pseudo-α-L-mannopyranose 86 as well as the C6-linkes dimer 81. The X-ray structureof dimer 30 with calcium has shown interesting molecular propertiesand cell-assembly. Molecular modeling of the higher oligomers has shown atendency toward secondary β-turn characteristics foundin polypeptide chains such as L-proline octamers. Based on the metal-chelatingability of some of the conjugates and the interesting secondary structuralproperties of L-chiro-inositol oligomers futuredirection of this research in the area of molecular recognition and combinatorialsynthesis are postulated.

  作者希望将这篇文章献给已故的沃尔夫冈·奥波尔泽教授，他于1996年3月15日逝世。奥波尔泽教授在有机合成艺术与工艺方面的贡献以及他充满活力的职业生涯因这场不幸的悲剧而戛然中止，这给合成化学界留下了一个严重的空白。他的思维能力和解决问题的方式为我们许多人树立了榜样和灵感。托马斯·赫德利奇卡在奥波尔泽教授学术生涯早期曾在日内瓦担任博士后研究员。他认为自己作为独立研究者的许多成就归功于1977-78年从奥波尔泽教授那里获得的指导；他深感失去了一位伟大的实践者。 来自氯或溴环己二烯-顺-二醇9的乙烯环氧18和31以及乙烯氮杂环24和25已经以迭代方式与保护的环醇19、37和46缩合，生成了二聚、三聚和四聚的环醇或氨基环醇偶联物，这些偶联物在进一步功能化烯烃和去保护后产生了肌醇偶联物22、53和59以及氨基环醇偶联物30、36和45。碘环己二烯-顺-二醇71和甲基莽草酸82被用作合成伪-β-D-吡喃葡萄糖85和伪-α-L-吡喃甘露糖86以及C6连接的二聚体81的前体。二聚体30与钙的X射线结构显示了有趣的分子性质和细胞组装。更高寡聚体的分子建模显示了类似于L-脯氨酸八聚体的二级β-转角特征。基于一些偶联物的金属螯合能力和L-手性肌醇寡聚体的有趣二级结构性质，关于分子识别和组合合成的未来研究方向被推测。
• Hudlicky, Tomas; Luna, Hector; Olivo, Horacio F., Journal of the Chemical Society. Perkin transactions I, 1991, # 12, p. 2907 - 2918
  作者：Hudlicky, Tomas、Luna, Hector、Olivo, Horacio F.、Andersen, Catherine、Nugent, Thomas、Price, John D.

  DOI：——

  日期：——
• Enantiospecific synthesis and insect feeding activity of sulfur-containing cyclitols
  作者：Ana Bellomo、Soledad Camarano、Carmen Rossini、David Gonzalez

  DOI：10.1016/j.carres.2008.09.026

  日期：2009.1

  The first syntheses of two deoxythiocyanocyclitols (4-deoxy-4-thiocyano-1-chiro-inositol and deoxythio-cyanoconduritol F) and two deoxysulfonylcyclitol acetals are reported by a chemoenzymatic enantioselective route. The compounds were prepared by a sequence of enzymatic and ruthenium-catalyzed dihydroxylations, and the results were studied regarding reaction conditions and co-catalyst for different derivatives. The new compounds were included in a minilibrary of deoxygenated cyclitols and evaluated for their capacity to influence the feeding behavior of Epilachna paenulata (Coleoptera: Coccinellidae), a common pest of the Curcubitaceae crops. (C) 2008 Elsevier Ltd. All rights reserved.
• Chemoenzymatic preparation of (6R)-5,6-dihydro-2H-pyran-2-one: a ubiquitous structural motif of biologically active lactones
  作者：Ignacio Carrera、Margarita Brovetto、Gustavo A. Seoane

  DOI：10.1016/j.tetasy.2013.10.005

  日期：2013.12

  A chemoenzymatic synthesis of an enantiopure 6-substituted 5,6-dihydro-2H-pyran-2-one using bromobenzene as a starting material is presented. This important structural motif is found in a large number of chiral lactones that present a wide range of biological activities. The key features of the preparation include enzymatic dioxygenation of bromobenzene using Escherichia coli JM109 (pDTG601), microwave-assisted acyloin cleavage, and tin mediated lactonization. The stereochemical assignment for the alcohol was confirmed by NMR analysis of Moshers derivatives. (C) 2013 Elsevier Ltd. All rights reserved.