1-Deoxy-3,4-O-isopropylidene-D-erythro-2-pentulofuranose | 138811-35-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-Deoxy-3,4-O-isopropylidene-D-erythro-2-pentulofuranose
• 英文别名: 1-deoxy-3,4-O-isopropylidene-D-ribulose；1-deoxy-3,4-O-isopropylidene-D-erythro-pentulofuranose；(3aR,6aR)-2,2,4-Trimethyltetrahydrofuro[3,4-d][1,3]dioxol-4-ol；(3aR,6aR)-2,2,4-trimethyl-6,6a-dihydro-3aH-furo[3,4-d][1,3]dioxol-4-ol
• CAS: 138811-35-5
• 化学式: C₈H₁₄O₄
• 分子量: 174.197
• InChiKey: CXFOHYBUJPCLDY-LPBDRPKESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.2
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  47.9
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1-Deoxy-3,4-O-isopropylidene-D-erythro-2-pentulofuranose 在 二异丁基氢化铝 作用下， 以 甲苯 为溶剂， 生成 (S)-1-((4S,5R)-5-hydroxymethyl-2,2-dimethyl-1,3-dioxolan-4-yl)ethanol 、 (R)-1-((4S,5R)-5-hydroxymethyl-2,2-dimethyl-1,3-dioxolan-4-yl)ethanol
  参考文献：
  名称：

  碳水化合物内酯的 2,3-O-异亚丙基衍生物衍生的半缩醛的非对映选择性还原

  摘要：

  有机镁和/或有机锂试剂与 2,3-O-异亚丙基-D-赤藓内酯和 5-O-叔丁基二苯基甲硅烷基 1-2,3-O-异亚丙基-D-核糖内酯的反应得到了相应的半缩醛的良好产率，通过氢化物试剂的选择，可以立体选择性地还原以产生在新手性中心和内酯的 C-2 之间具有顺式（苏式）关系的产物。

  DOI：

  10.1246/cl.1996.67
• 作为产物：
  描述：

  ((3aR,6aR)-4-Hydroxy-2,2-dimethyl-tetrahydro-furo[3,4-d][1,3]dioxol-4-yl)-acetic acid ethyl ester 在 氢氧化钾 作用下， 生成 1-Deoxy-3,4-O-isopropylidene-D-erythro-2-pentulofuranose
  参考文献：
  名称：

  吡喃类和呋喃类醛内酯与氯甲基三甲基硅烷衍生试剂的反应

  摘要：

  摘要吡喃类和呋喃类醛内酯与三甲基甲硅烷基甲基锂的反应为碳链加长的甲基酮的合成提供了一条方便的途径。内酯与氯代（三甲基甲硅烷基）甲基-锂反应，得到相应的氯代甲基酮。

  DOI：

  10.1016/0008-6215(91)80007-a

文献信息

• Amadori ketoses with calcium hydroxide and the Kiliani reaction on 1-deoxy ketoses: two approaches to the synthesis of saccharinic acids
  作者：David J. Hotchkiss、Sarah F. Jenkinson、Richard Storer、Thomas Heinz、George W.J. Fleet

  DOI：10.1016/j.tetlet.2005.11.018

  日期：2006.1

  aldonic acids) may be formed by treatment of Amadori ketoses with calcium hydroxide or by the Kiliani reaction of 1-deoxy ketoses with cyanide. Thus (i) N,N-dibenzyl or N,N-dimethyl-1-amino-1-deoxy-d-fructose with aqueous calcium hydroxide afforded 2-C-methyl-d-ribono-1,4-lactone under green conditions and (ii) reaction of methyl magnesium bromide with 2,3-O-isopropylidene-d-erythronolactone gave 1-deoxy-3

  可以通过用氢氧化钙处理Amadori酮糖或通过1-脱氧酮糖与氰化物的Kiliani反应来形成糖精酸（2- C-甲基醛糖酸）。因此，（i）N，N-二苄基或N，N-二甲基-1-氨基-1-脱氧-d-果糖与氢氧化钙水溶液在绿色条件下得到2 - C-甲基-d-核糖-1,4-内酯。 （ii）使甲基溴化镁与2，3 - O-异亚丙基-d-异乙内酯反应，得到1-脱氧-3，4- O-异亚丙基-d-核糖，随后用氰化钠水溶液处理并水解， 2 C-甲基-d-阿拉伯糖基-1,4-内酯。这样的支链糖内酯可能具有作为含有支链碳链的Chirons的价值。
• Anomeric stereospecific synthesis of 2′-C-methyl β-nucleosides; the Holy reaction of cyanamide with 2-C-methyl-d-arabinose
  作者：Sarah F. Jenkinson、Nigel A. Jones、Adel Moussa、Alistair J. Stewart、Thomas Heinz、George W.J. Fleet

  DOI：10.1016/j.tetlet.2007.04.105

  日期：2007.6

  of 2-C-methyl-d-arabinose with cyanamide and methyl propiolate afford an anhydronucleoside, which may be opened under acid conditions with inversion at C2′, to give 2′-C-methyl uridine; ring opening with sodium hydroxide gave 2′-C-methyl arabino-uridine with retention of configuration at C2′. This gives complete stereospecific control to yield only β-nucleosides.

  2 - C-甲基-d-阿拉伯糖与氰酰胺和丙酸甲酯的顺序反应提供了脱水核苷，其可以在酸性条件下打开并在C2'处转化，得到2'- C-甲基尿苷；用氢氧化钠开环得到2'- C-甲基阿拉伯糖-尿苷，其在C2'处的构型得以保留。这提供了完全的立体定向控制，仅产生β-核苷。
• Carbon-branched carbohydrate chirons: synthesis of C-3 and C-4-branched sugar lactones derived from d-erythronolactone
  作者：Sarah F. Jenkinson、K. Victoria Booth、Amalia M. Estévez Reino、Graeme Horne、Ramón J. Estévez、George W.J. Fleet

  DOI：10.1016/j.tetasy.2009.08.029

  日期：2009.10

  Two carbon chain extensions using a Wittig reaction on both a 1-deoxy ribulose derivative and a C-2-branched erythrose derivative are reported. Subsequent dihydroxylation resulted in the synthesis of C-3 and C-4 methyl-branched sugar lactones, the useful synthetic building blocks. Control of the stereoselectivity of both the Wittig reaction and the dihydroxylation is investigated, and 3-C-methyl and

  报道了使用Wittig反应在1-脱氧核糖衍生物和C-2-支化赤藓糖衍生物上的两个碳链延伸。随后的二羟基化作用导致合成了C-3和C-4甲基支链糖内酯，它们是有用的合成构件。研究了Wittig反应和二羟基化反应的立体选择性的控制，并研究了3- C-甲基和4- C-甲基d-altrono-1,4-内酯和d-glucono-1,4-内酯和4- C合成了-羟甲基-d-altrono-1,4-内酯。
• Doubly carbon-branched pentoses: synthesis of both enantiomers of 2,4-di-C-methyl arabinose and 2-deoxy-2,4-di-C-methyl arabinose using only acetonide protection
  作者：K. Victoria Booth、Sarah F. Jenkinson、Daniel Best、Fernando Fernández Nieto、Ramón J. Estévez、Mark R. Wormald、Alexander C. Weymouth-Wilson、George W.J. Fleet

  DOI：10.1016/j.tetlet.2009.06.098

  日期：2009.9

  An acetonide is the only protecting group used in the synthesis of both the enantiomers of 2,4-di-C-methyl arabinose and 2-deoxy-2,4-di-C-methyl arabinose via the enantiomeric 3-C-methyl-L-erythronolactone [from 2-C-methyl-D-ribono-lactone or D-ribose] and 3-C-methyl-D-erythronolactone [from D-tagatose Or L-ribose]. NMR studies on unprotected C-methyl arabinoses show that methyl branching significantly affects the ratios of pyranose and furanose forms present in aqueous Solution. (C) 2009 Elsevier Ltd. All rights reserved.
• Total Synthesis and Absolute Configuration of Pseudosemiglabrin, a Platelet Aggregation Antagonist, and Its Diastereomer Semiglabrin
  作者：Michael C. Pirrung、Yong Rok Lee

  DOI：10.1021/ja00122a011

  日期：1995.5

  A general approach to the synthesis of the flavone-furo[2,3-b]furan ring system present in numerous biologically-active secondary metabolites of Tephrosia sp. has been developed and applied in one racemic synthesis and two asymmetric syntheses of four members of the family. It uses 2-diazo-1,3-cyclohexanedione as the keystone of the ring system, uniting it with a dihydrofuran through a rhodium-mediated dipolar cycloaddition. The enolate of this tricyclic intermediate is then utilized to elaborate a salicylate that is subjected to a concise annulation protocol with benzaldehyde to produce the tetracycle. Stereochemical control is accomplished by the use of three strategies. Reduction of a ketone from the more accessible face of a folded bicyclooctane ring system produces the endo stereochemistry. Steric hindrance by a bulky allylic siloxy group directs the cycloaddition to the opposite face of the prochiral alkene to generate the exo stereochemistry. Finally, a novel hydroxyl-directed cycloaddition simultaneously produces the endo stereochemistry and accesses the opposite enantiomeric series.