(1RS,2SR,3RS,4RS)-2,3-dibromocyclohex-5-ene-1,4-diol | 169529-93-5

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 卤代醇
• 英文名称: (1RS,2SR,3RS,4RS)-2,3-dibromocyclohex-5-ene-1,4-diol
• 英文别名: (1RS,4RS,5SR,6SR)-5,6-dibromocycloxex-2-ene-1,4-diol；rac-(1S,4S,5R,6R)-5,6-dibromocyclohex-2-ene-1,4-diol；5beta,6alpha-Dibromo-2-cyclohexene-1beta,4alpha-diol；(1S,4S,5R,6R)-5,6-dibromocyclohex-2-ene-1,4-diol
• CAS: 169529-93-5
• 化学式: C₆H₈Br₂O₂
• 分子量: 271.936
• InChiKey: DHMGPRNBMJDWOM-UNTFVMJOSA-N

物化性质

• 沸点：
  372.6±42.0 °C(Predicted)
• 密度：
  2.220±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  10
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 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：

  (1RS,2SR,3RS,4RS)-2,3-dibromocyclohex-5-ene-1,4-diol 在 吡啶 作用下， 反应 12.0h， 生成 (+)-(1S,2R,3R,4S)-1,4-diacetoxy-2,3-dibromocyclohex-5-ene
  参考文献：
  名称：

  Enzyme-Assisted Total Synthesis of the Optical Antipodes d-myo-Inositol 3,4,5-Trisphosphate and d-myo-Inositol 1,5,6-Trisphosphate:  Aspects of Their Structure−Activity Relationship to Biologically Active Inositol Phosphates

  摘要：

  Unambiguous total syntheses of bath optical antipodes of the enantiomeric pair D-myo-inositol 3,4,5-trisphosphate (Ins(3,4,5)P-3) and D-myo-inositol 1,5,6-trisphosphate (Ins(1,5,6)P-3) are described. The ring system characteristic of myo-inositol was constructed de novo from p-benzoquinone. X-ray data for the enzymatically resolved (1S,2R,3R,4S)-1,4-diacetoxy-2,3-dibromocyclohex-5-ene enabled the unequivocal assignment of the absolute configuration. Subsequent transformations under stereocontrolled conditions led to enantiopure C-2-symmetrical 1,4-(di-O-benzyldiphospho)conduritol B derivatives. Their synthetic potential was exploited to prepare Ins(3,4,5,6)P-4 and Ins(1,4,5,6)P-4 in three steps. With a recently identified and partially purified InsP(5)/InsP(4) phosphohydrolase from Dictyostelium discoideum, these enantiomers could be converted to the target compounds, Ins(3,4,5)P-3 and Ins(1,5,6)P-3, on a preparative scale. An HPLC system employed for both purification of the inositol phosphates and analytical runs ensured that the products were isomerically homogeneous. The sensitivity of detection achieved by a complexometric postcolumn derivatization method indicates that the complexation properties of Ins(3,4,5)P-3/Ins(1,5,6)P-3 resemble those of Ins(1,2,3)P-3, a compound with antioxidantpotential. The set of inositol phosphates synthesized was used to clarify structural motifs important for molecular recognition by p42(IP4) , high-affinity Ins(1,3,4,5)P-4/PtdIns(3,4,5)P-3-specific binding protein from pig cerebellum.

  DOI：

  10.1021/jm981113k
• 作为产物：
  描述：

  (+)-(1S,2R,3R,4S)-1,4-diacetoxy-2,3-dibromocyclohex-5-ene 在 titanium(IV) isopropylate 、 异丙醇 作用下， 以92%的产率得到(1RS,2SR,3RS,4RS)-2,3-dibromocyclohex-5-ene-1,4-diol
  参考文献：
  名称：

  Enzymic Resolution of a C2 Symmetric Diol Derived from p-Benzoquinone: Synthesis of (+)- and (-)-Bromoxone

  摘要：

  DOI：

  10.1021/jo00126a012

文献信息

• Concerning the reaction of anti-benzene dioxide with various nucleophiles
  作者：Thomas Esser、Frédéric Farkas、Sissi Mangholz、Urs Séquin

  DOI：10.1016/s0040-4020(01)90392-8

  日期：1994.3

  6-Diepoxycyclohex-1-ene (anti-benzene dioxide) (5) was brought into reaction with several S, O, and C nucleophiles. S and O nucleophiles gave the bis-adducts stemming from independent reaction of the two epoxy functions. C nucleophiles, on the other hand, led to 1,4-addition products. A deuterium labelling experiment showed that BuLi added to the vinyloxirane part of 5 rather than to the conjugated diepoxide

  使反式-3,4：5,6-二环氧环己-1-烯（抗二氧化苯）（5）与几个S，O和C亲核试剂反应。S和O亲核试剂产生了由两个环氧官能团的独立反应产生的双加合物。另一方面，C亲核试剂产生1，4-加成产物。氘标记实验表明，BuLi添加到5的乙烯基环氧乙烷部分中，而不是添加到共轭二环氧官能团上，产生顺式加合物。像预期的那样，铜酸盐主要产生反式产物。
• Chemical Synthesis and Self-Assembly of a Ladderane Phospholipid
  作者：Jaron A. M. Mercer、Carolyn M. Cohen、Steven R. Shuken、Anna M. Wagner、Myles W. Smith、Frank R. Moss、Matthew D. Smith、Riku Vahala、Alejandro Gonzalez-Martinez、Steven G. Boxer、Noah Z. Burns

  DOI：10.1021/jacs.6b10706

  日期：2016.12.14

  producing organism and the inherent difficulty of purifying complex lipid mixtures have prohibited isolation of useful amounts of natural ladderane lipids. We have devised a highly selective total synthesis of ladderane lipid tails and a full phosphatidylcholine to enable biophysical studies on chemically homogeneous samples of these molecules. Additionally, we report the first proof of absolute configuration

  厌氧氨氧化细菌产生的梯烷脂质构成了生物膜脂质中结构最吸引人但研究很少的分子。生产生物的缓慢生长和纯​​化复杂脂质混合物的固有困难阻碍了有用量的天然梯烷脂质的分离。我们设计了一种高度选择性的梯烷脂尾部和全磷脂酰胆碱的全合成，以实现对这些分子的化学均质样品的生物物理研究。此外，我们报告了天然梯烷的绝对构型的第一个证明。
• Regio- and stereospecific synthesis of dl-4,5-dibromo-4,5-dideoxy-3,6-O-methyl-chiro-inositol
  作者：Latif Kelebekli、Kadir Aksu、Ertan Şahin

  DOI：10.1016/j.tetlet.2018.02.050

  日期：2018.3

  The regio- and stereospecific synthesis of dl-4,5-dibromo-4,5-dideoxy-3,6-O-methyl-chiro-inositol is reported. Bromination of p-benzoquinone followed by reduction of the carbonyl groups with NaBH4 gave the corresponding trans-dibromodiol compound, which was reacted with sodium methoxide to produce dimethoxy conduritol-B. Regiospecific bromination of the alkene moiety furnished the desired chiro-inositol

  报道了dl -4，5-二溴-4，5-二脱氧-3，6- O-甲基-手性肌醇的区域和立体有择合成。对-苯醌的溴化，然后用NaBH 4还原羰基，得到相应的反式-二溴二醇化合物，其与甲醇钠反应生成二甲氧基Conduritol-B。烯烃部分的区域特异性溴化提供了所需的手性肌醇衍生物。
• Concise syntheses and some biological activities of <scp>dl</scp> ‐2,5‐di‐ <i>O</i> ‐methyl‐ <i>chiro</i> ‐inositol, <scp>dl</scp> ‐1,4‐di‐ <i>O</i> ‐methyl‐ <i>scyllo</i> ‐inositol, and <scp>dl</scp> ‐1,6‐dibromo‐1,6‐dideoxy‐2,5‐di‐ <i>O</i> ‐methyl‐ <i>chiro</i> ‐inositol
  作者：Kadir Aksu、Hulya Akincioglu、Ilhami Gulcin、Latif Kelebekli

  DOI：10.1002/ardp.202000254

  日期：2021.2

  stereospecific synthesis of O-methyl-chiro-inositols and O-methyl-scyllo-inositol was achieved, starting from p-benzoquinone. After preparing dimethoxy conduritol-B as a key compound, regiospecific bromination of the alkene moiety of dimethoxy conduritol-B and acid-catalyzed ring opening of dimethoxydiacetate conduritol-B epoxide with Ac2 O afforded the desired new chiro-inositol derivatives and scyllo-inositol

  从对苯醌开始，实现了 O-甲基-手性肌醇和 O-甲基-鲨肌醇的区域和立体定向合成。在制备二甲氧基硬糖醇-B作为关键化合物后，二甲氧基硬糖醇-B的烯烃部分的区域特异性溴化和二甲氧基二乙酸硬糖醇-B环氧化物与Ac2O的酸催化开环得到所需的新手性肌醇衍生物和鲨肌醇衍生物， 分别。光谱方法用于表征所有合成的化合物。新型肌醇 (11-17) 对人碳酸酐酶同工酶 I 和 II（hCA I 和 II）以及乙酰胆碱酯酶 (AChE) 具有有效的抑制特性。发现新型肌醇 11-17 是针对 AChE、hCA I 和 hCA II 酶的有效抑制剂。Ki 值的计算范围为 87。hCA I 为 59 ± 7.011 至 237.95 ± 17.75 μM，hCA II 为 65.08 ± 12.39 至 538.98 ± 61.26 μM，A.7Ch 分别为 193.28 ± 43.13 至 765.08 ± 209
• Asymmetric Induction of Conduritols via AAA Reactions: Synthesis of the Aminocyclohexitol of Hygromycin A
  作者：Barry M. Trost、Joseph Dudash, Jr.、Erik J. Hembre

  DOI：10.1002/1521-3765(20010417)7:8<1619::aid-chem16190>3.0.co;2-4

  日期：2001.4.17

  Two synthetic routes towards the construction of the aminocyclohexitol moiety of hygromycin A have been developed based on palladium-catalyzed asymmetric alkylation of conduritol derivatives. A protocol has been established whereby this biologically relevant molecule is formed from benzoquinone. A conduritol A derivative is synthesized in eight steps from benzoquinone and is then subjected to the palladium

  基于钯催化的Conduritol衍生物的不对称烷基化，已开发出两种构建潮霉素A氨基环己糖醇部分的合成途径。已经建立了一种方案，由此该生物学上相关的分子由苯醌形成。从苯醌以八个步骤合成Conduritol A衍生物，然后进行钯反应。从这种柔性中间体中，可以得到具有完全立体选择性的氨基环醇的四种差向异构体，包括天然的一种。外消旋的conduritol B衍生物可从苯醌中分四个步骤获得，然后通过钯催化的动态动力学拆分将其对映体纯。氨基环糖醇可以从手性调和醇B中分六步获得。