ethyl 2,6-anhydro-3-deoxy-4,5:7,8-di-O-isopropylidene-D-glycero-D-talo-octanoate | 109150-98-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: ethyl 2,6-anhydro-3-deoxy-4,5:7,8-di-O-isopropylidene-D-glycero-D-talo-octanoate
• 英文别名: ethyl 2,6-anhydro-3-deoxy-4,5:7,8-di-O-isopropylidene-D-glycero-D-talo-octonate；Ethyl 2,6-anhydro-3-deoxy-4,5:7,8-di-isopropylidene-D-glycero-D-talo-octonate；ethyl 2,6-anhydro-3-deoxy-D-glycero-D-talooctonate；ethyl (3aR,4R,6S,7aR)-4-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-2,2-dimethyl-4,6,7,7a-tetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-6-carboxylate
• CAS: 109150-98-3
• 化学式: C₁₆H₂₆O₇
• 分子量: 330.378
• InChiKey: JNMKXCPYQRYQGV-NZEXEKPDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  23
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.94
• 拓扑面积：
  72.4
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  ethyl 2,6-anhydro-3-deoxy-4,5:7,8-di-O-isopropylidene-D-glycero-D-talo-octanoate 在 三氟乙酸 作用下， 以 乙醇 为溶剂， 反应 1.0h， 生成 (2R,4R,5R)-6-((R)-1,2-Dihydroxy-ethyl)-4,5-dihydroxy-tetrahydro-pyran-2-carboxylic acid ethyl ester
  参考文献：
  名称：

  New synthesis of a CMP-KDO synthetase inhibitor and of 2-deoxy-KDO derivatives used in the synthesis of such inhibitors

  摘要：

  DOI：

  10.1021/jo00228a057
• 作为产物：
  描述：

  2,3,5,6-di-isopropyIidene-1,4-dihydroxy-D-mannitol 在 palladium dihydroxide 咪唑 、 氢气 、 碘 、 sodium hydride 、 三苯基膦 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 反应 10.25h， 生成 ethyl 2,6-anhydro-3-deoxy-4,5:7,8-di-O-isopropylidene-D-glycero-D-talo-octanoate
  参考文献：
  名称：

  A new synthesis of 2-deoxy-β-Kdo, a potent CMP-Kdo synthetase inhibitor

  摘要：

  DOI：

  10.1016/0008-6215(92)84119-d

文献信息

• Condensation of D-mannosaldehyde derivatives with ethyl diazoacetate. An easy and stereoselective chain elongation methodology for carbohydrates: Application to new syntheses for KDO and 2-deoxy-β-KDO
  作者：Fidel J López-Herrera、Francisco Sarabia-García

  DOI：10.1016/s0040-4020(97)00056-2

  日期：1997.3

  (3R and 3S) beta-Hydroxy-alpha-diazocarbonyl compounds 4(100%, 3:2), 9 (35%, 100:0), 14 (74%, 7:2) and 18 (100%. 100:0), prepared from 2,3,4.5.6-penta-O-acetyl- (3), penta-O-benzyl- (8), 2.3:5,6-di-O-isopropylidene-4-O-(tert-bulyldimethylsilyl)- (13), and 2.3:5,6-di-0-isopropylidene-4-0-acetyl-D-mannosaldehyde (17), respectively, were acetylated, and the resulting beta-ncetoxy-alpha-diazocarbonpl compounds treated with rhodium diacetate to give the corresponding-alpha-enolesters,6 (100%). 11 (35%), 16(100%)and 20 (100%),which are potentially alpha-ketoesiers. Molecularmechanics calculations were used in order to justify the stereoselectivity observed in the initial addition process. The problematic removal of the protecting groups from the alpha-keto esters is discussed. Finally, hydrazinolysis of the cc-enol acetates (to quench the labile resulting a-keto ester as the corresponding and less reactive hydrazines), mild oxidation to the corresponding alpha-diazoesters, deprotection, and final oxidation of the diazo group with m-chloroperhenzoic acid, gave KDO in good yield. Intermediate products were used in the completely stereoselective synthesis of 2-deoxy-beta-KDO, a potent inhibitor for CMP-KDO synthetase. (C) 1997 Published by Elsevier Science Ltd.

  三氢群（3R和3S）的β-羟基-α-重氮甲酰化合物4（100%，3:2）、9（35%，100:0）、14（74%，7:2）和18（100%，100:0），分别由2,3,4,5,6-五-O-乙酰基-（3）、五-O-苄基-（8）、2,3,5,6-二-O-异丙基二酮基-4-O-(叔丁基二甲基硅基)-（13）、以及2,3,5,6-二-O-异丙基二酮基-4-O-乙酰基-D-甘醛（17）制备而成，随后这些化合物被乙酰化。得到的β-乙酰氧基-α-重氮甲酰化合物经二乙酸铑处理，生成相应的α-烯醇酯6（100%）、11（35%）、16（100%）和20（100%），这些化合物可能是α-酮酸酯。为了验证初始加成过程中观察到的立体选择性，进行了分子力学计算。文中讨论了从α-酮酸酯中去除保护基团的难点。最后，通过肼解α-烯醇乙酰酯（以淬灭不稳定的产物α-酮酸酯，生成相应的羟胺，活性较低），进行温和氧化生成对应的α-重氮酸酯，解保护，并最终使用邻氯过苯甲酸氧化重氮基团，成功制得KDO，产量良好。中间产物被用于完全立体选择性合成2-去氧-β-KDO，该化合物是CMP-KDO合成酶的强效抑制剂。 （C）1997 由Elsevier Science Ltd出版。
• A new synthesis for 2-deoxy-KDO, a potent inhibitor of CMP=KDO synthetase
  作者：Francisco Sarabia-García、Fidel J. López-Herrera、María S. Pino-González

  DOI：10.1016/s0040-4039(00)73474-5

  日期：1994.9

  A new synthesis for the 2-deoxy KDO 2 by aldolic condensation of 2,3:5,6-di-O-isopropylidene-4-acetyl-D-manno aldehyde 4 with ethyl diazoacetate and conversion of the condensation product to the 3-deoxy-2-diazo ester 13 in four steps is reported. Rhodium (II) decomposition of the diazo compound leads to the α-anomer of the 2-deoxy pyranose 14 stereospecifically. Removla of isopropylidene groups and

  2,3：5,6-二-O-异亚丙基-4-乙酰基-D-甘露糖醛4与重氮乙酸乙酯的醛基缩合合成2-脱氧KDO 2的新方法，并将缩合产物转化为3-报道了四个步骤中的脱氧-2-重氮酯13。重氮化合物的铑（II）分解导致2-脱氧吡喃糖14的α-异构体立体定向。除去异亚丙基和酯水解可提供2，这是CMP-KDO合成酶的有效抑制剂。
• Efficient Large Scale Syntheses of 3-Deoxy-<scp>d</scp>-manno-2-octulosonic acid (Kdo) and Its Derivatives
  作者：Yingle Feng、Jie Dong、Fangyuan Xu、Aiyun Liu、Li Wang、Qi Zhang、Yonghai Chai

  DOI：10.1021/acs.orglett.5b00901

  日期：2015.5.15

  An efficient method to rapidly synthesize 3-deoxy-d-manno-2-octulosonic acid (Kdo) and its derivatives in large scale has been developed. Starting from d-mannose, the di-O-isopropylidene derivative of Kdo ethyl ester was prepared in three steps on a scale of more than 40 g in one batch in an overall yield of 75–80% without any intermediate purification. Kdo, Kdo glycal, and 2-acetylated Kdo ester were

  快速高效的方法合成3-脱氧d -manno -2-辛酮糖酸（KDO）及其在大规模衍生物已被开发。从d-甘露糖开始，分三批以超过40 g的规模分三步制备Kdo乙酯的二-O-异亚丙基衍生物，总产率为75-80％，无需任何中间纯化。由Kdo乙酯的二-O-异亚丙基衍生物快速高产率地合成了Kdo，Kdo糖基和2-乙酰化的Kdo酯。通过使用t - BuOH作为质子源，通过α-异构体的差向异构化，以高立体选择性获得2-脱氧-β-Kdo酯。
• Synthesis of ld-Hepp and KDO containing di- and tetrasaccharide derivatives of Neisseria meningitidis inner-core region via iodonium ion promoted glycosidations
  作者：G.J.P.H. Boons、F.L. van Delft、P.A.M. van der Klein、G.A. van der Marel、J.H. van Boom

  DOI：10.1016/s0040-4020(01)88191-6

  日期：——

  The synthesis of methyl(ethyl) 2-thio-KDO (i.e. 1, 2, 5, 7 and 10) and ethyl 1-thio-LD-Hepp (i.e. 26 and 43) derivatives will be described. The latter derivatives proved to be suitable donors in iodonium ion (NIS/IFOH) promoted glycosidation reactions. The usefulness of the glycosidation approach was illustrated by the successful conclusion of a spacer containing dimer L-alpha-D-Hepp-(1 --> 5)-alpha-KDO-2-O-(CH2)3NH2 (37) and tetramer beta-D-Galp-(1 --> 4)-beta-D-Glep-(1 --> 4)-L-alpha-D-Hepp-(1 -->5)-alpha-KDO-2-O-(CH2)3NH2 (47).
• LUTHMAN, KRISTINA;ORBE, MARTIN;WAGLUND, TOMMY;CLAESSON, ALF, J. ORG. CHEM., 52,(1987) N 17, 3777-3784
  作者：LUTHMAN, KRISTINA、ORBE, MARTIN、WAGLUND, TOMMY、CLAESSON, ALF

  DOI：——

  日期：——