2-deoxy-3,4:6,7-di-O-isopropylidene-D-glycero-manno-heptono-1,5-lactone | 130481-65-1

• 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-deoxy-3,4:6,7-di-O-isopropylidene-D-glycero-manno-heptono-1,5-lactone
• 英文别名: 2-deoxy-3,4:6,7-di-O-isopropylidene-D-manno-heptono-1,5-lactone；2-deoxy-3,4:6,7-di-O-isopropylidene-D-manno-heptonic acid 1,5-lactone；(3aR,4R,7aR)-4-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-2,2-dimethyl-3a,4,7,7a-tetrahydro-[1,3]dioxolo[4,5-c]pyran-6-one
• CAS: 130481-65-1
• 化学式: C₁₃H₂₀O₆
• 分子量: 272.298
• InChiKey: UXHSJUSYRJAFHP-YJFSRANCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  19
• 可旋转键数：
  1
• 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-deoxy-3,4:6,7-di-O-isopropylidene-D-glycero-manno-heptono-1,5-lactone 在 sodium hydroxide 、 二甲基硫 、 叔丁基锂 、 臭氧 、 溶剂黄146 作用下， 反应 2.75h， 生成 3-deoxy-α-D-manno-oct-2-ulosonic acid
  参考文献：
  名称：

  Asymmetric Syn-Selective Aldol Reactions of γ-Oxygenated Vinylogous Urethane with a Second Generation Chiral Auxiliary:  Application in Construction of (+)-3-Deoxy-d-manno-2-octulosonic Acid

  摘要：

  Various examples of highly diastereoselective aldol reactions are presented where the nonracemic lithium enolate 6 derived from a C4-oxygenated vinylogous urethane reacts in syn fashion to provide upon intramolecular lactonization useful gamma-alkoxy-delta-lactone synthons 12a-f. In one particular example, the result of reaction with an acrolein surrogate, the lactone product 12e is applied in an efficient asymmetric synthesis of(+)-KDO (10 steps, 34% overall yield). Notable transformations include (1) hydrolysis of the vinylogous urethane functionality, (2) stereoselective reduction of the resulting beta-keto-lactone 2, (3) stereoselective dihydroxylation of the vinyl side chain of delta-lactone 17, and (4) addition of alpha-ethoxy-vinyllithium to the lactone carbonyl of 19 to procure the aldulosonic acid residue in 1 upon ozonolysis.

  DOI：

  10.1021/jo981916f
• 作为产物：
  描述：

  3,4:6,7-di-O-isopropylidene-2-O-trifluoromethanesulphonyl-D-glycero-D-talo-heptono-1,5-lactone 在 lithium iodide 作用下， 以 四氢呋喃 为溶剂， 以85%的产率得到2-deoxy-3,4:6,7-di-O-isopropylidene-D-glycero-manno-heptono-1,5-lactone
  参考文献：
  名称：

  由糖内酯合成高度取代的环戊烷的还原性醇醛策略

  摘要：

  碘离子诱导受保护的5-甲酰基-2-碘-1,5-内酯进行还原性羟醛缩合，以中等收率得到完全取代的环戊烷衍生物。这种策略可以提供诸如甘露他汀和别甲唑啉等高度功能化的碳环的一般合成。

  DOI：

  10.1016/0040-4039(91)80795-8

文献信息

• A New Short and Efficient Route to 3-Deoxy-<scp>d</scp>-<i>manno</i>-oct-2-ulosonic Acid (KDO) and 3-Deoxy-<scp>d</scp>-<i>arabino</i>-hept-2-ulosonic Acid (DAH)
  作者：Richard Plantier-Royon、Charles Portella、Vincent Kikelj

  DOI：10.1055/s-2006-926375

  日期：——

  An efficient synthesis of lactones 5 and 6, known intermediates towards KDO and DAH, respectively, has been achieved by a short and highly efficient route. Homologation of protected D-mannose and D-arabinose was performed by a Peterson reaction with 2-lithio-2-trimethylsilyldithiane or the corresponding bis(methylsulfanyl) derivative, followed by the cyclization of the resulting ketene dithioacetal

  内酯 5 和 6 的有效合成，分别是 KDO 和 DAH 的已知中间体，已通过一条短而高效的路线实现。受保护的 D-甘露糖和 D-阿拉伯糖的同系化是通过与 2-锂硫-2-三甲基甲硅烷基二噻烷或相应的双（甲硫基）衍生物的彼得森反应进行的，然后在非常平稳的条件下环化得到的乙烯酮二硫缩醛。用碘进行氧化处理以高产率的三步顺序得到内酯 5 和 6。有趣的是，这种方法可以被认为是合成各种 2-脱氧糖内酯的通用方法。
• General syntheses of ethyl 2-ulosonates and 3-deoxy-D-manno-oct-2-ulosonic acid from carbohydrate lactones with 1-ethoxyvinyllithium
  作者：Shende Jiang、Anthony D. Rycroft、Gurdial Singh、Xiang-Zhu Wang、Yu-Lin Wu

  DOI：10.1016/s0040-4039(98)00590-5

  日期：1998.5

  Reactions of 1-ethoxyvinyllithium with isopropylidene or benzyl protected sugar lactones afforded the corresponding hemiacetals which, on ozonolysis, gave the ethyl 2-ulosonates. This allowed a rapid and efficient synthesis of 3-deoxy-d-manno-oct-2-ulosonic acid (KDO).

  1-乙氧基乙烯基锂与异亚丙基或苄基保护的糖内酯的反应得到相应的半缩醛，其在臭氧分解中得到2-磺基乙酯。这允许快速且有效地合成3-脱氧-d-甘露糖-辛基-2-磺酸（KDO）。
• A Stereocontrolled approach to 3-deoxy-d-manno-2-octulosonic acid containing disaccharides
  作者：Arnaud Haudrechy、Pierre Sinaÿ

  DOI：10.1016/s0040-4039(00)97952-8

  日期：1990.1

  The development of a synthetic approach to KDO containing disaccharides based on stereocontrolled iodocyclization of an enol ether is detailed.

  详细介绍了基于烯醇醚的立体控制碘环化合成含KDO的二糖合成方法的过程。
• A practical synthesis of 2-deoxy aldonolactones via a SmI2-mediated α-deoxygenation reaction
  作者：Stephen Hanessian、Christian Girard、Jose Luis Chiara

  DOI：10.1016/s0040-4039(00)92313-x

  日期：1992.1

  A one-step deoxygenation of 2-hydroxylactones or their acetates is possible using samarium diiodide as an electron-transfer reagent in conjunction with a proton source.
• Cyclization of hydroxy enol ethers: a stereocontrolled approach to 3-deoxy-D-manno-2-octulosonic acid containing disaccharides
  作者：Arnaud Haudrechy、Pierre Sinay

  DOI：10.1021/jo00041a017

  日期：1992.7

  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.