2,3:4,6-di-O-isopropylidene-D-mannono-1,5-lactone | 143289-36-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氧吡喃
• 英文名称: 2,3:4,6-di-O-isopropylidene-D-mannono-1,5-lactone
• 英文别名: (1R,2S,6S,9R)-4,4,12,12-tetramethyl-3,5,8,11,13-pentaoxatricyclo[7.4.0.02,6]tridecan-7-one
• CAS: 143289-36-5
• 化学式: C₁₂H₁₈O₆
• 分子量: 258.271
• InChiKey: GAWJWSHHBYXDLM-HXFLIBJXSA-N

物化性质

• 熔点：
  199-201 °C(Solv: ethyl acetate (141-78-6); water (7732-18-5))
• 沸点：
  365.4±42.0 °C(Predicted)
• 密度：
  1.167±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  18
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  63.2
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  2,3:4,6-di-O-isopropylidene-D-mannono-1,5-lactone 在 四氯化碳 、 三(二甲胺基)膦 作用下， 反应 2.0h， 以90%的产率得到1-chloro-1-deoxy-2,3:4,6-di-O-isopropylidene-D-ribo-hex-1-enopyranose
  参考文献：
  名称：

  Unusual behaviour of some γ- and δ-lactones towards dichloromethylenation using tris(dimethylamino)phosphine–tetrachloromethane

  摘要：

  Lactones derived from D-glucose, D-mannose and L-ascorbic acid reacted unexpectedly with tris-(dimethylamino)phosphine-tetrachloromethane to give, respectively, dichloroalkene, anomeric vinyl chloride or acyl chloride; this behaviour supports an ionic mechanism for the alkenation.

  DOI：

  10.1039/p19920001471
• 作为产物：
  描述：

  在 palladium on activated charcoal 草酰氯 、 氢气 、 二甲基亚砜 、 三乙胺 作用下， 以 乙醇 为溶剂， 反应 48.0h， 生成 2,3:4,6-di-O-isopropylidene-D-mannono-1,5-lactone
  参考文献：
  名称：

  Synthesis of 1-deoxy-l-gulonojirimycin (l-guloDNJ) and 1-deoxy-d-talonojirimycin (d-taloDNJ)

  摘要：

  Carbohydrate based syntheses of azasugars with unusual configurations viz. 1,5-dideoxy-1,5-imino-L-gulitol (L-gulo DNJ) and 1,5-dideoxy-1,5-imino-L-talitol (L-talo DNJ) are reported, from D-mannose and D-fructose, respectively. The key steps in both syntheses involved reductive aminative cyclizations. Thus, L-gulo DNJ was obtained by reduction of 2,3;4,6-di-O-isopropylidene-5-O-p-toluenesulfonyl-D-mannononitrile with LiAlH4 in DME to give the protected azasugar which upon hydrolysis with HCl afforded crystalline L-guloDNJ as the HCl salt in 29% overall yield. Reduction of 6-azido-1-O-tert-butyldimethylsityl-2,3-O-isopropylidene-beta-D-ribohexulofuranose obtained from D-fructose in six steps, followed by treatment with HCl, afforded L-talo DNJ as an HCl salt in similar to10% overall yield. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0008-6215(02)00100-3

文献信息

• Efficient conditions for the synthesis of C-glycosylidene derivatives: a direct and stereoselective route to C-glycosyl compounds
  作者：Y Lakhrissi、C Taillefumier、M Lakhrissi、Y Chapleur

  DOI：10.1016/s0957-4166(99)00586-8

  日期：2000.2

  Efficient conditions for the synthesis of C-glycosylidene compounds from lactones based on Wittig reactions of cyanomethyl triphenylphosphoranylidene involving microwave heating are described: subsequent stereoselective reduction of the anomeric olefins gave the corresponding C-glycosides in good yields with high stereocontrol.

  描述了基于氰基甲基三苯基磷杂亚烷基的涉及微波加热的Wittig反应从内酯合成C-糖基亚基化合物的有效条件：随后的异头烯烃的立体选择性还原以良好的收率和高的立体控制得到了相应的C-糖苷。
• Chemistry of 1-Alkoxy-1-glycosyl Radicals:  Formation of β-Mannopyranosides by Radical Decarboxylation and Decarbonylation of <i>manno</i>-Heptulosonic Acid Glycoside Derivatives
  作者：David Crich、Jae-Taeg Hwang、Hongwei Yuan

  DOI：10.1021/jo960799q

  日期：1996.1.1

  A method for the preparation of highly enriched beta-mannopyranosides is described. A glycosyl donor 28 is prepared from tetraallyl mannonolactone by standard means and coupled to a number of primary carbohydrate alcohols, resulting in the isolation in excellent yields of axial disaccharides. Following exchange of the allyl groups for acetyl esters, the furan is oxidatively cleaved with catalytic RuO(2)

  描述了一种制备高度浓缩的β-甘露聚糖的方法。通过标准方法由四烯丙基甘露糖内酯制备糖基供体28，并将其与许多伯糖醇偶联，从而以极高的产率获得了轴向二糖。在将烯丙基交换为乙酰基酯后，呋喃被催化RuO（2）和NaIO（4）氧化裂解，所得酸经过Barton脱羧。28与仲醇2,3-异亚丙基-α-L-鼠李糖吡喃糖苷的偶合导致异头异构体化学结构的明显倒置和赤道二糖的分离。
• Discovery of a Phosphine-Mediated Cycloisomerization of Alkynyl Hemiketals: Access to Spiroketals and Dihydropyrazoles via Tandem Reactions
  作者：Jaideep Saha、Chris Lorenc、Bikash Surana、Mark W. Peczuh

  DOI：10.1021/jo3001854

  日期：2012.4.20

  functionality (R2) on the cyclic keto enol ether, a rapid and facile dimerization occurs, giving spiroketal products. When the enone is substituted (i.e., R2 = Ph), the cyclic keto enol ether is sufficiently stable so that it can be isolated; it can then be further reacted in the same pot to provide the corresponding dihydropyrazoles. Both the spiroketal and dihydropyrazole products arise by a tandem reaction

  这里报道的是关于膦催化的半缩酮的异构化以及环状酮-烯醇醚产物的后续反应的详细信息。新的环异构化是对先前报道的胺催化过程的补充，该过程从相同的半缩醛起始原料制得了环氧庚烷酮。在环状酮烯醇醚上不存在官能团（R 2）的情况下，发生快速且容易的二聚，得到螺缩酮产物。当烯酮被取代时（即R 2=），则环状酮烯醇醚足够稳定，因此可以将其分离出来；然后可以将其在同一罐中进一步反应以提供相应的二氢吡唑。螺环酮和二氢吡唑产物均通过串联反应产生，该串联反应始于新的环异构化。该方法允许从相对简单的起始材料快速引入产品的复杂性。它应在天然产物样分子的合成中找到应用。
• Synthesis of Pyranoid and Furanoid Glycals from Glycosyl Sulfoxides by Treatment with Organolithium Reagents
  作者：Ana M. Gómez、Marta Casillas、Aitor Barrio、Anna Gawel、J. Cristóbal López

  DOI：10.1002/ejoc.200800318

  日期：2008.8

  Glycosyl sulfoxides can be conveniently transformed into pyranoid or furanoid glycals by treatment with organolithium reagents. The more likely reaction pathway involves a sulfoxide/metal exchange reaction to generate a glycosyllithium derivative that undergoes β-elimination of its C-2 substituent. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

  通过用有机锂试剂处理，糖基亚砜可以方便地转化为吡喃或呋喃糖。更可能的反应途径涉及亚砜/金属交换反应以生成糖基锂衍生物，该衍生物经历其 C-2 取代基的 β-消除。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)
• Enantioselective synthesis of structurally intricate and complementary polyoxygenated building blocks of Spongistatin 1 (Altohyrtin A)
  作者：Alain Braun、Il Hwan Cho、Stephane Ciblat、Dean Clyne、Pat Forgione、Amy C. Hart、Guoxiang Huang、Jungchul Kim、Isabelle Modolo、Leo A. Paquette、Xiaowen Peng、Stefan Pichlmair、Catherine A. Stewart、Jizhou Wang、Dmitry Zuev

  DOI：10.1135/cccc2008181

  日期：——

  Enantioselective approaches to the construction of four complex building blocks of the structurally intricate marine macrolide known as spongistatin 1 are presented. The first phase of the synthetic effort relies on a practical approach to a desymmetrized, enantiomerically pure spiroketal ring system incorporating rings A and B. Concurrently, the C17–C28 subunit, which houses one-fifth of the stereogenic centers of the target in the form of rings C and D, was assembled via a composite of stereocontrolled aldol condensations. Once arrival at the entire C1–C28 sector had been realized, routes were devised to provide two additional highly functionalized sectors consisting of C29–C44 and C38–C51. A series of subsequent transformations including cyclization of the E ring and hydroboration to afford the B-alkyl intermediate for the key Suzuki coupling to append the side chain took advantage of efficient stereocontrol. Ultimately, complete assembly and functionalization of the western EF sector of spongistatin was thwarted by an inoperative Suzuki coupling step intended to join the side chain to the C29–C44 sector, and later because of complications due to protecting groups, which precluded the complete elaboration of the late stage C29–C51 intermediate.

  提出了构建结构复杂的海洋大环内酯素丝孢菌素1的四个复杂构建模块的对映选择性方法。合成工作的第一阶段依赖于一种实用方法，用于构建包含环A和B的非对称、对映纯的螺环糖环系统。同时，C17-C28亚单位，其中包含目标物中五分之一的立体中心，以环C和D的形式组装，通过立体控制的醛缩合反应组合而成。一旦完成整个C1-C28区段的合成，就设计了提供C29-C44和C38-C51两个额外高度官能化区段的路线。随后的一系列转化反应包括E环的环化和氢硼化反应，以获得用于关键的铃木偶联的B-烷基中间体，利用了高效的立体控制。最终，丝孢菌素的西部EF区段的完整组装和官能化受挫于无法进行的铃木偶联步骤，该步骤旨在将侧链连接到C29-C44区段，后来由于保护基的复杂性导致无法完全展开晚期C29-C51中间体。