6-deoxy-L-mannose diphenyldithioacetal | 30571-61-0

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: 6-deoxy-L-mannose diphenyldithioacetal
• 英文别名: (2R,3R,4S,5S)-1,1-bis(phenylsulfanyl)hexane-2,3,4,5-tetrol
• CAS: 30571-61-0
• 化学式: C₁₈H₂₂O₄S₂
• 分子量: 366.502
• InChiKey: XPGWYLWXDRKROM-KKBVYLPWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  24
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  132
• 氢给体数：
  4
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  6-deoxy-L-mannose diphenyldithioacetal 在 N-溴代丁二酰亚胺(NBS) 作用下， 以 丙酮 为溶剂， 反应 3.5h， 生成 2,3,4,5-tetra-O-acetyl-6-deoxy-L-mannose
  参考文献：
  名称：

  Application of molecular mechanics in the total stereochemical elucidation of spicigerolide, a cytotoxic 6-tetraacetyloxyheptenyl-5,6-dihydro-α-pyrone from Hyptis spicigera

  摘要：

  Bioactivity-directed fractionation of the crude extract prepared from the medicinal Mexican plant Hyptis spicigera (Lamiaceae) tested on KB cells led to the isolation of spicigerolide (1). The structure for this novel cytotoxic compound was elucidated as 6R-[3S,4S,5S,6S-tetraacetyloxy-1Z-heptenyl]-5,6-dihydro-2H-pyran-2-one. The relative stereochemistry of this flexible molecule was determined by a combination of molecular mechanics calculations and H-1-H-1 coupling constant data, while the absolute configuration was established according to CD measurements. The MM/(3)J(H-H) calculations, as applied to 1, was validated with model Linear compounds prepared from L-rhamnose: 2,3,4,5-tetra-O-acetyl-6-deoxy-L-mannose (5) and tetra-O-acetyl-1,6-dideoxy-L-mannitol (8). Both compounds possess the same stereochemistry predicted to be present in the acyclic moiety of spicigerolide (1) but lacking the stereochemical influence of the chiral pyrone. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(00)00987-x
• 作为产物：
  描述：

  L-rhamnopyranose 、 苯硫酚 在 盐酸 作用下， 生成 6-deoxy-L-mannose diphenyldithioacetal
  参考文献：
  名称：

  糖无环衍生物的构型

  摘要：

  摘要2,3,4,5-四-O-乙酰基-醛-d-核糖（1），其d-阿拉伯糖（2），d-木糖（3）和d-lyxo（4）类似物和2在氯仿溶液中，通过100 nm的nmr光谱研究了1,3,4,5-四-O-乙酰基-6-脱氧-醛基-1-半乳糖（5）。分配所有质子的信号，并通过自旋解耦进行验证，并确定一阶耦合常数。这些化合物的有利构象显示为扩展的平面锯齿形形式2，除非这种构象将导致成对的取代基之间发生黯淡的1,3-相互作用，在这种情况下，有利的构象是“镰刀形”形式3–5，其中1,3-相互作用通过绕链的碳-碳键旋转而减轻，从而得到不同的旋转异构体状态。2,3的二苯基二硫缩醛（分别为8和9），制备了4，5-四-O-乙酰基-d-木糖和2,3,4,5-四-O-乙酰基-6-脱氧-1-甘露糖，并对其构象进行了研究；事实证明，与二乙基类似物相比，氯化汞对这些化合物的脱巯基化更困难。

  DOI：

  10.1016/s0008-6215(00)88011-8

文献信息

• Regioselective Dehydration of Sugar Thioacetals under Mild Conditions
  作者：Rachel Szpara、Alexander Goyder、Michael J. Porter、Helen C. Hailes、Tom D. Sheppard

  DOI：10.1021/acs.orglett.1c00424

  日期：2021.4.2

  are abundant in waste biomass, making them sustainable chiral building blocks for organic synthesis. The demand for chiral saturated heterocyclic rings for pharmaceutical applications is increasing as they provide well-defined three-dimensional frameworks that show increased metabolic resistance. A range of sugar thioacetals can be dehydrated selectively at C-2 under mild basic conditions, and the

  糖类在废弃生物质中含量丰富，使它们成为有机合成的可持续手性构件。药物应用对手性饱和杂环的需求正在增加，因为它们提供了明确的三维框架，显示出更高的代谢抗性。一系列糖硫缩醛可以在温和的碱性条件下在 C-2 处选择性脱水，所得的烯酮硫缩醛可以通过进一步的选择性脱水反应用于生产有用的手性结构单元。
• Banuelos-Hernandez; Mendoza-Espinoza, South African Journal of Chemistry, 2012, vol. 65, p. 84 - 90
  作者：Banuelos-Hernandez、Mendoza-Espinoza

  DOI：——

  日期：——
• Fragoso-Serrano, Mabel; Guillen-Jaramillo, Georgina; Pereda-Miranda, Rogelio, Journal of Organic Chemistry, 2003, vol. 68, # 19, p. 7167 - 7175
  作者：Fragoso-Serrano, Mabel、Guillen-Jaramillo, Georgina、Pereda-Miranda, Rogelio、Cerda-Garcia-Rojas, Carlos M.

  DOI：——

  日期：——
• Conformation of acyclic derivatives of sugars
  作者：D. Horton、J.D. Wander

  DOI：10.1016/s0008-6215(00)88011-8

  日期：1970.11

  in which case the favored conformation is a “sickle” form 3–5 in which the 1,3-interaction is alleviated, by rotation about a carbon-carbon bond of the chain, to give a different rotameric state. The diphenyl dithioacetals ( 8 and 9 , respectively) of 2,3,4,5-tetra- O -acetyl- d -lyxose and 2,3,4,5-tetra- O -acetyl-6-deoxy- l -mannose were prepared, and their conformations studied; demercaptalation

  摘要2,3,4,5-四-O-乙酰基-醛-d-核糖（1），其d-阿拉伯糖（2），d-木糖（3）和d-lyxo（4）类似物和2在氯仿溶液中，通过100 nm的nmr光谱研究了1,3,4,5-四-O-乙酰基-6-脱氧-醛基-1-半乳糖（5）。分配所有质子的信号，并通过自旋解耦进行验证，并确定一阶耦合常数。这些化合物的有利构象显示为扩展的平面锯齿形形式2，除非这种构象将导致成对的取代基之间发生黯淡的1,3-相互作用，在这种情况下，有利的构象是“镰刀形”形式3–5，其中1,3-相互作用通过绕链的碳-碳键旋转而减轻，从而得到不同的旋转异构体状态。2,3的二苯基二硫缩醛（分别为8和9），制备了4，5-四-O-乙酰基-d-木糖和2,3,4,5-四-O-乙酰基-6-脱氧-1-甘露糖，并对其构象进行了研究；事实证明，与二乙基类似物相比，氯化汞对这些化合物的脱巯基化更困难。
• Application of molecular mechanics in the total stereochemical elucidation of spicigerolide, a cytotoxic 6-tetraacetyloxyheptenyl-5,6-dihydro-α-pyrone from Hyptis spicigera
  作者：Rogelio Pereda-Miranda、Mabel Fragoso-Serrano、Carlos M Cerda-Garcı́a-Rojas

  DOI：10.1016/s0040-4020(00)00987-x

  日期：2001.1

  Bioactivity-directed fractionation of the crude extract prepared from the medicinal Mexican plant Hyptis spicigera (Lamiaceae) tested on KB cells led to the isolation of spicigerolide (1). The structure for this novel cytotoxic compound was elucidated as 6R-[3S,4S,5S,6S-tetraacetyloxy-1Z-heptenyl]-5,6-dihydro-2H-pyran-2-one. The relative stereochemistry of this flexible molecule was determined by a combination of molecular mechanics calculations and H-1-H-1 coupling constant data, while the absolute configuration was established according to CD measurements. The MM/(3)J(H-H) calculations, as applied to 1, was validated with model Linear compounds prepared from L-rhamnose: 2,3,4,5-tetra-O-acetyl-6-deoxy-L-mannose (5) and tetra-O-acetyl-1,6-dideoxy-L-mannitol (8). Both compounds possess the same stereochemistry predicted to be present in the acyclic moiety of spicigerolide (1) but lacking the stereochemical influence of the chiral pyrone. (C) 2000 Elsevier Science Ltd. All rights reserved.