6,7-O-isopropylidene-2,3-dideoxy-4-thio-D-arabino-hept-2-enono-1,4-lactone | 164025-12-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 6,7-O-isopropylidene-2,3-dideoxy-4-thio-D-arabino-hept-2-enono-1,4-lactone
• 英文别名: 6,7-O-isopropylidene-4-thio-2,3,4-trideoxy-D-arabino-hept-2-enonic acid 1,4-thiolactone；(5R)-5-((R)-[((4R)-2,2-dimethyl-1,3-dioxolan-4-yl)hydroxymethyl])-5H-thiophen-2-one；(2R)-2-[(R)-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-hydroxymethyl]-2H-thiophen-5-one
• CAS: 164025-12-1
• 化学式: C₁₀H₁₄O₄S
• 分子量: 230.285
• InChiKey: PIBIEMXUMLFSFB-ZXFLCMHBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.4
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  81.1
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  6,7-O-isopropylidene-2,3-dideoxy-4-thio-D-arabino-hept-2-enono-1,4-lactone 在 2,6-二甲基吡啶 、 sodium tetrahydroborate 、 sodium periodate 、 silica gel 、 溶剂黄146 、 N,N-二异丙基乙胺 、 nickel dichloride 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 6.0h， 生成 (1R,4S,5R,6R)-5,6-bis-(tert-butyldimethylsilanyloxy)-2-thiabicyclo[2.2.1]heptan-3-one
  参考文献：
  名称：

  Variable Strategy toward Carbasugars and Relatives. 2.¹ Diversity-Based Synthesis of β-d-Xylo, β-d-Ribo, β-l-Arabino, and β-l-Lyxo 4a-Carbafuranoses and (4a-Carbafuranosyl)thiols

  摘要：

  The silyloxy diene-based construction of carbasugars, previously exploited for the synthesis of four carbocyclic furanose and pyranose analogues, has been investigated further. By introducing a novel silylative cycloaldolization protocol and by adjusting a couple of minor transformations, the efficiency of this synthetic sequence was greatly improved. Through a series of lactone/thiolactone aldehyde cyclization precursors, four carbafuranoses (4a-carba-beta -D-xylofuranose, 4a-carba-beta -D-ribofuranose, 4a-carba-beta -L-arabinofuranose, and 4a-carba-beta -L-lyxofuranose) and four (carbafuranosyl)thiols [(4a-carba-beta -D-xylofuranosyl)thiol, (4a-carba-beta -D-ribofuranosyl)thiol, (4a-carba-beta -L-arabinofuranosyl)thiol, and (4a-carba-beta -L-lyxofuranosyl)thiol] were assembled. From this study, it was shown that these constructions tolerate a variety of precursors, and in many instances, they are suitable for scaling-up.

  DOI：

  10.1021/jo010585v
• 作为产物：
  描述：

  双丙酮-D-甘露糖醇 在 sodium periodate 、 三氟化硼乙醚 、 silica gel 作用下， 以 二氯甲烷 、 水 为溶剂， 反应 4.5h， 生成 6,7-O-isopropylidene-2,3-dideoxy-4-thio-D-arabino-hept-2-enono-1,4-lactone
  参考文献：
  名称：

  呋喃基，吡咯基和噻吩基的2-甲硅烷氧基二烯的实用性，通过无水产乙酸原素核心单元及其吡咯烷和噻吩类似物的模块化合成得到证明。

  摘要：

  我们报告了一种模块化的策略，用于获取无水产乙酸原素的核心单元及其氮和硫类似物，从而产生了巨大的结构多样性。该合成是基于重复性乙烯基加成方案的应用，该方案涉及独特的三联甲硅氧基二烯模块，2-[（叔丁基二甲基甲硅烷基）氧基]呋喃（TBSOF），N-（叔丁氧基羰基）-2-[（叔） -丁基二甲基甲硅烷基）氧基]吡咯（TBSOP）和2-[（叔丁基二甲基甲硅烷基）氧基]噻吩（TBSOT）和合适的杂原子稳定的碳正离子。通过将TBSOF，TBSOP和TBSOT亲核合成子与某些四氢呋喃，吡咯烷和硫杂环戊烷受体结合，可以确保构建与杂色产乙酸原素的核心片段相关的各种相邻相邻的寡杂环基序。首先，通过组装涵盖所有氧，氮和硫杂原子组合（即化合物7-9、13-15和19-21）的18个模型构造的集合，验证了枢轴耦合操纵的可靠性。然后，该统一的方案适用于伪造高级双-四氢呋喃，双-吡咯烷和双-硫杂环戊烷支架，这些支架涵盖了

  DOI：

  10.1021/jo991568x

文献信息

• Expeditious Syntheses of Sugar-Modified Nucleosides and Collections Thereof Exploiting Furan-, Pyrrole-, and Thiophene-Based Siloxy Dienes
  作者：Gloria Rassu、Franca Zanardi、Lucia Battistini、Enrico Gaetani、Giovanni Casiraghi

  DOI：10.1021/jm960400q

  日期：1997.1.1

  enriched 2',3'-dideoxynucleosides 14a-c (alpha and beta anomers of L- and D-series), 2',3'-dideoxy-4'-thionucleosides 21a-c (alpha and beta anomers of L- and D-series), and 2',3'-dideoxy-4'-azanucleosides 28a-c (beta anomers of L- and D-series) were synthesized, with uniform chemistry and high stereochemical efficiency, exploiting a triad of versatile heterocyclic siloxy dienes, namely, 2-(tert-but

  一系列单独的糖修饰的嘧啶核苷，包括对映体富集的2'，3'-二脱氧核苷14a-c（L和D系列的α和β端基异构体），2'，3'-二脱氧-4'-硫代核苷21a-合成了c（L和D系列的α和β端基异构体）和2'，3'-二脱氧-4'-氮杂核苷28a-c（L和D系列的β端基异构体）立体化学效率，利用三元组的多功能杂环甲硅烷氧基二烯，即2-（叔丁基二甲基甲硅烷氧基）呋喃（TBSOF），2-（叔丁基二甲基甲硅烷氧基）噻吩（TBSOT）和N-（叔丁氧基羰基）-2-（叔丁基二甲基甲硅烷氧基）吡咯（TBSOP）。合成方法有利地使用甘油醛丙酮化物的对映体（D-1和L-1）作为手性来源和甲酰基阳离子的合成等同物。
• Furan-, Pyrrole-, and Thiophene-Based Siloxydienes for Syntheses of Densely Functionalized Homochiral Compounds
  作者：Giovanni Casiraghi、Gloria Rassu

  DOI：10.1055/s-1995-3983

  日期：1995.6

  This review describes the methods of preparation and use of 2-(trimethylsiloxy)furan, N-(tert-butoxycarbonyl)-2-(tert-butyldimethylsiloxy)pyrrole, and certain substituted analogues and congeners, including novel 2-(tert-butyldimethylsiloxy)thiophene, to synthesize complex carbohydrates, azasugars, polyhydroxylated alkaloids, C-glycosylated α-amino acids, amino acids bearing quaternary chiral carbon atoms, and thiosugars. Especially emphasized is the preparation of enantiomerically pure compounds of biological interest. Some mechanistic insights are presented.

  本综述介绍了 2-(三甲基硅氧基)呋喃、N-(叔丁氧羰基)-2-(叔丁基二甲基硅氧基)吡咯以及某些取代的类似物和同系物的制备和使用方法，包括新型 2-(叔丁基二甲基硅氧基)噻吩、包括新型 2-(叔丁基二甲基硅氧基)噻吩，以合成复杂的碳水化合物、氮杂糖、多羟基生物碱、C-糖基化 δ±-氨基酸、含有季手性碳原子的氨基酸和硫代糖。特别强调的是制备具有生物学意义的对映体纯化合物。还介绍了一些机理方面的见解。
• 2-(tert-butyldimethylsiloxy)thiophene: Application to total syntheses of both enantiomers of 2′,3′-dideoxy-4′-thiocytidine
  作者：Gloria Rassu、Pietro Spanu、Luigi Pinna、Franca Zanardi、Giovanni Casiraghi

  DOI：10.1016/0040-4039(95)00162-6

  日期：1995.3

  Exploiting novel 2-(tert-butyldimethylsiloxy)thiophene (1, TBSOT) as versatile carbon nucleophile and both enantiomers of glyceraldehyde acetonide as chiral sources, an entry to both enantiomers of anti HIV-active 2′,3′-dideoxy-4′-thiocytidine 10 and ent-10 was devised and executed.

  利用新型2-（叔丁基二甲基甲硅烷氧基）噻吩（1，TBSOT）作为通用的碳亲核试剂和甘油醛丙酮化物的两种对映体作为手性来源，这两种抗HIV活性2'，3'-dideoxy-4'-的对映体均进入设计并执行了硫胞苷10和ent-10 。
• Parallel, Stereoselective Syntheses of both Enantiomers of Muricatacin and Their Sulfur and Nitrogen Relatives Using the Silyloxy Diene-Based Methodology
  作者：Gloria Rassu、Luigi Pinna、Pietro Spanu、Franca Zanardi、Lucia Battistini、Giovanni Casiraghi

  DOI：10.1021/jo970205z

  日期：1997.6.1
• Variable Strategy toward Carbasugars and Relatives. 2.¹ Diversity-Based Synthesis of β-<scp>d</scp>-Xylo, β-<scp>d</scp>-Ribo, β-<scp>l</scp>-Arabino, and β-<scp>l</scp>-Lyxo 4a-Carbafuranoses and (4a-Carbafuranosyl)thiols
  作者：Gloria Rassu、Luciana Auzzas、Luigi Pinna、Vincenzo Zambrano、Lucia Battistini、Franca Zanardi、Lucia Marzocchi、Domenico Acquotti、Giovanni Casiraghi

  DOI：10.1021/jo010585v

  日期：2001.11.1

  The silyloxy diene-based construction of carbasugars, previously exploited for the synthesis of four carbocyclic furanose and pyranose analogues, has been investigated further. By introducing a novel silylative cycloaldolization protocol and by adjusting a couple of minor transformations, the efficiency of this synthetic sequence was greatly improved. Through a series of lactone/thiolactone aldehyde cyclization precursors, four carbafuranoses (4a-carba-beta -D-xylofuranose, 4a-carba-beta -D-ribofuranose, 4a-carba-beta -L-arabinofuranose, and 4a-carba-beta -L-lyxofuranose) and four (carbafuranosyl)thiols [(4a-carba-beta -D-xylofuranosyl)thiol, (4a-carba-beta -D-ribofuranosyl)thiol, (4a-carba-beta -L-arabinofuranosyl)thiol, and (4a-carba-beta -L-lyxofuranosyl)thiol] were assembled. From this study, it was shown that these constructions tolerate a variety of precursors, and in many instances, they are suitable for scaling-up.