(2R,3R,4R,5R)-1,2:4,5-di-O-isopropylidene-hept-6-ene-1,2,3,4,5-pentol | 137945-76-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (2R,3R,4R,5R)-1,2:4,5-di-O-isopropylidene-hept-6-ene-1,2,3,4,5-pentol
• 英文别名: (R)-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl][(4S,5R)-2,2-dimethyl-5-vinyl-1,3-dioxolan-4-yl]methanol；1,2-dideoxy-3,4:6,7-di-O-isopropylidene-D-manno-hept-1-enitol；(R)-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl][(4S,5R)-5-ethenyl-2,2-dimethyl-1,3-dioxolan-4-yl]methanol；(R)-((R)-2,2-dimethyl-1,3-dioxolan-4-yl)((4S,5R)-2,2-dimethyl-5-vinyl-1,3-dioxolan-4-yl)methanol；1,2-dideoxy-3,4:6,7-bis-O-(isopropylidene)-D-manno-hept-1-enitol；(R)-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-[(4S,5R)-5-ethenyl-2,2-dimethyl-1,3-dioxolan-4-yl]methanol
• CAS: 137945-76-7
• 化学式: C₁₃H₂₂O₅
• 分子量: 258.315
• InChiKey: ZQUFIYCCFZOXLJ-GWOFURMSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  57.2
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (2R,3R,4R,5R)-1,2:4,5-di-O-isopropylidene-hept-6-ene-1,2,3,4,5-pentol 在 吡啶 、 sodium hydroxide 、 9-borabicyclo[3.3.1]nonane dimer 、 双氧水 、 pyridinium chlorochromate 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 8.75h， 生成 2,6-anhydro-1,3-dideoxy-4,5:7,8-di-O-isopropylidene-D-manno-oct-1-enitol
  参考文献：
  名称：

  Cyclization of hydroxy enol ethers: a stereocontrolled approach to 3-deoxy-D-manno-2-octulosonic acid containing disaccharides

  摘要：

  A method for the preparation of the carboxylic acids 14 and 15 has been developed, starting from known 2,3,5,6-di-O-isopropylidene-D-mannofuranose. Esterification of 14 and 15 with methanol, methyl 2,3,4-tri-O-benzyl-alpha-D-glucopyranoside, and 1,2,5,6-di-O-isopropylidene-alpha-D-glucofuranose, followed by reaction with Tebbe reagent and selective deprotection gave, respectively, the key complex hydroxy enol ethers 20, 26, and 35. Stereoselective iodocyclization, followed by transformation of the CH2I appendage into a methyloxycarbonyl group, gave the corresponding protected KDO-containing disaccharides.

  DOI：

  10.1021/jo00041a017
• 作为产物：
  描述：

  甘露糖 在 potassium tert-butylate 、 碘 作用下， 以 四氢呋喃 为溶剂， 反应 49.0h， 生成 (2R,3R,4R,5R)-1,2:4,5-di-O-isopropylidene-hept-6-ene-1,2,3,4,5-pentol
  参考文献：
  名称：

  来自 d-甘露糖的 6-Amino-2,6-dideoxy-α-Kdo 的全合成。

  摘要：

  3-脱氧d -甘露-辛-2-糖酸（KDO）生物合成途径是在抗菌药物发现有希望的靶点。在此，我们报告了 6-氨基-2,6-双脱氧-α-Kdo 在 15 个步骤中从d-甘露糖作为 Kdo 加工酶的潜在抑制剂的全合成。合成序列的关键步骤包括用于双碳链同源化的 Horner-Wadsworth-Emmons 反应，然后是 6 -exo-trig Pd 催化的还原环化或串联 Staudinger/aza-Wittig 反应，同时伴随 α-亚氨基酯还原，使类似 Kdo 的六元氮杂环的α-立体选择性形成成为可能。

  DOI：

  10.1021/acs.orglett.0c01847

文献信息

• Stereoselective Total Synthesis of Siladenoserinols A and D
  作者：Yinxin Liu、Jun Liu、Chuanfang Zhao、Yuguo Du

  DOI：10.1021/acs.orglett.1c00720

  日期：2021.5.7

  The stereoselective total synthesis of siladenoserinols A and D has been accomplished using carbohydrate as a chiral template. The feature of this work is to build the medicinally privileged 6,8-DOBCO scaffold through a cascade reaction of hydrogenation/deacetalization/ketalization in a one-pot process, that is, to take advantage of a thermodynamically controlled bicyclization of polyhydroxyketone

  使用碳水化合物作为手性模板已经完成了硅腺芥子醇A和D的立体选择性全合成。这项工作的特点是通过一锅法中加氢/脱缩醛/缩酮化的级联反应来构建具有医学优势的6,8-DOBCO支架，即利用HCl / MeOH反应条件。当前的具有成本效益的合成策略可以促进硅腺苷丝氨酸的生物活性研究。
• Synthesis of Enantiomerically Pure Eight- and Nine-Membered Lactones by Copper(I) Chloride/2,2’-Bipyridine-Catalyzed Cyclization
  作者：Frank O.H. Pirrung、Henk Hiemstra、W. Nico Speckamp、Bernard Kaptein、Hans E. Schoemaker

  DOI：10.1055/s-1995-4429

  日期：1995.4

  The stereocontrolled formation of eight- and nine-membered lactones by Cu(I)Cl/2,2’-bipyridine-catalyzed atom transfer cyclization of enantiomerically pure oxygen-substituted ω-alkenyl di- and trichloroacetates is described. The lactones are formed exclusively via the endo-cyclization mode and generally show a characteristic cis-relationship between the C-5 and C-6 substituents due to a highly stereoselective ring closure and chlorine transfer.

  本文描述了通过铜(I)氯/2,2'-联吡啶催化的手性氧取代的β-烯基二氯和三氯乙酸酯的原子转移环化反应，实现了八元和九元内酯的立体控制合成。这些内酯的形成完全是通过endo-环化模式，并且由于高度立体选择性的环闭合和氯转移，通常表现出C-5和C-6取代基之间的特征性顺式关系。
• Formal Synthesis of 3-Deoxy-d-manno-Octulosonic Acid (KDO) and 3-Deoxy-d-arabino-2-heptulosonic Acid (DAH)
  作者：Kwok Mong、Tapan Pradhan、Chun Lin

  DOI：10.1055/s-0032-1317932

  日期：——

  synthetic routes to 3-deoxy- d - manno -octulo­sonic acid (KDO) and 3-deoxy- d - arabino -2-heptulosonic acid (DAH) from common sugar substrates are reported. Chain homologation of the sugar substrates was accomplished by Wittig olefination and Corey–Fuchs alkynylation. A new cyclization strategy was investigated to access the desired pyranosyl isomer of the KDO target.

  报道了从常见糖底物合成 3-脱氧-d-甘露糖-辛糖酸 (KDO) 和 3-脱氧-d-阿拉伯糖-2-庚糖酸 (DAH) 的实用合成路线。糖底物的链同源化是通过 Wittig 烯化和 Corey-Fuchs 炔化完成的。研究了一种新的环化策略以获取所需的 KDO 目标吡喃糖基异构体。
• 1,4-Diazabicyclo[2.2.2]octane (DABCO) - an Efficient Reagent in the Synthesis of Alkyl Tosylates or Sulfenates
  作者：Jens Hartung、Siegfried Hünig、Rainer Kneuer、Michaela Schwarz、Hermann Wenner

  DOI：10.1055/s-1997-1372

  日期：1997.12

  The bicyclic tertiary amine 1,4-diazabicyclo[2.2.2]octane (DABCO) is a promising substitute not only for the widely used but hazardous and hygroscopic base pyridine in the syntheses of alkyl tosylates 3 but also for triethylamine in the preparation of alkyl sulfenates 4 from sterically hindered alcohols 2. In several provided examples the substrates 2 were completely converted into the desired products, e.g. the respective tosylates 3, which minimized subsequent separation processes. The current protocol points, in a number of cases, to nonchlorinated solvents as good alternatives to chloroform or dichloromethane and offers a workup procedure for a larger scale reaction which relies on the removal of the side products by filtration instead of the traditional extraction method using several aqueous washings.

  双环三级胺1,4-二氮杂双环[2.2.2]辛烷（DABCO）不仅是广泛使用但具有危险性和吸湿性的基础物质吡啶在合成烷基托烯酯3中的有希望的替代品，也是三乙胺在从空间位阻的醇2制备烷基亚硫酸酯4时的替代品。在提供的几个例子中，底物2被完全转化为所需的产物，例如相应的托烯酯3，从而最小化了后续的分离过程。目前的方案在多个案例中指出非氯化溶剂是氯仿或二氯甲烷的良好替代品，并提供了一种适用于大规模反应的后处理程序，该程序依赖于通过过滤去除副产物，而不是传统的使用多次水洗的提取方法。
• An expeditious route to the synthesis of highly functionalized chiral oxepines from monosaccharides
  作者：Huib Ovaa、Michiel A Leeuwenburgh、Herman S Overkleeft、Gijs A van der Marel、Jacques H van Boom

  DOI：10.1016/s0040-4039(98)00324-4

  日期：1998.5

  olefination of the anomeric center followed by either allylation or oxopalladation of alkoxy-1,2-propadienes is described. Ring-closing metathesis of the linear dienes gives rise to a variety of highly functionalized and chiral ring-expanded oxepines.

  描述了通过端基中心的Wittig烯化，然后烯丙基化或氧代丙二酸酯化烷氧基-1，2-丙二烯，将部分保护的醛基呋喃糖酶转变成二烯。线性二烯的闭环易位产生了各种高度官能化的和手性的环扩展的氧杂环丁烷。