1,2,5,6-di-isopropylidene-3,4-di-O-<(S-methyl)thiocarbonyl>-D-mannitol | 66401-14-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1,2,5,6-di-isopropylidene-3,4-di-O-<(S-methyl)thiocarbonyl>-D-mannitol
• 英文别名: 1,2:5,6-Di-O-isopropylidene-3,4-di-O-<(S-methylthio)thiocarbonyl>-D-mannitol；1,2:5,6-di-O-isopropylidene-3,4-bis-O-<(S-methylthio)thiocarbonyl>-D-mannitol；1,2:5,6-di-O-isopropylidene-3,4-bis-O-[(methylthio)thiocarbonyl]-D-mannitol；O-[(1R,2R)-1,2-bis[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-2-methylsulfanylcarbothioyloxyethyl] methylsulfanylmethanethioate
• CAS: 66401-14-7
• 化学式: C₁₆H₂₆O₆S₄
• 分子量: 442.643
• InChiKey: HUJRIBVONBHBAS-DDHJBXDOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  26
• 可旋转键数：
  9
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  170
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  1,2,5,6-di-isopropylidene-3,4-di-O-<(S-methyl)thiocarbonyl>-D-mannitol 在 sodium formate 、 sodium carbonate 、 (Bu₄N)₂S₂O₈ 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 1.0h， 以86%的产率得到(2S,3E,5S)-1,2,5,6-tetrahydroxy-1,2:5,6-di-O-isopropylidene-hex-3-ene
  参考文献：
  名称：

  用过氧化二硫酸四丁铵和甲酸根离子对醇进行轻松的Barton-McCombie脱氧。

  摘要：

  [反应：请参见文字]。描述了一种用于醇的有效自由基脱氧的新方法，用于制备散装化学品以避免规模扩大的问题。用（Bu（4）N）（2）S（2）O（8）和HCO（2）Na在DMF中处理各种硫代羰基衍生物以优异的收率提供了相应的脱氧产物。脱氧似乎是由单个电子从CO（2）（*）（-）而不是SO4（*）（-）转移到硫代羰基衍生物而引发的。

  DOI：

  10.1021/ol050886h
• 作为产物：
  描述：

  二硫化碳 、 双丙酮-D-甘露糖醇 、 碘甲烷 在 咪唑 、 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 以90%的产率得到1,2,5,6-di-isopropylidene-3,4-di-O-<(S-methyl)thiocarbonyl>-D-mannitol
  参考文献：
  名称：

  用过氧化二硫酸四丁铵和甲酸根离子对醇进行轻松的Barton-McCombie脱氧。

  摘要：

  [反应：请参见文字]。描述了一种用于醇的有效自由基脱氧的新方法，用于制备散装化学品以避免规模扩大的问题。用（Bu（4）N）（2）S（2）O（8）和HCO（2）Na在DMF中处理各种硫代羰基衍生物以优异的收率提供了相应的脱氧产物。脱氧似乎是由单个电子从CO（2）（*）（-）而不是SO4（*）（-）转移到硫代羰基衍生物而引发的。

  DOI：

  10.1021/ol050886h

文献信息

• The invention of radical reactions. Part XXXI. Diphenylsilane: a reagent for deoxygenation of alcohols via their thiocarbonyl derivatives, deamination via isonitriles, and dehalogenation of bromo- and iodo- compounds by radical chain chemistry
  作者：Derek H.R. Barton、Doo Ok Jang、Joseph Cs. Jaszberenyi

  DOI：10.1016/s0040-4020(01)87198-2

  日期：1993.8

  Various thionocarbonates and xanthates of alcohols and bis-xanthates of vic-diols are readily deoxygenated to the corresponding hydrocarbons or olefins, while bromides and iodides are dehalogenated with diphenylphenylsilane in good yield.

  各种thionocarbonates和醇的黄原酸盐和二的-xanthates VIC -diols容易脱氧成相应的烃或烯烃，而溴化物和碘化物与以良好的收率diphenylphenylsilane脱卤。
• Towards dideoxynucleosides: the silicon approach
  作者：Derek H.R. Barton、Doo Ok Jang、Joseph Cs. Jaszberenyi

  DOI：10.1016/s0040-4039(00)78787-9

  日期：1991.6

  Dixanthates, formed from vic-diols, can easily be transformed to the corresponding olefins with diphenylsilane in a new, high-yielding radical reaction.
• The invention of radical reactions. Part XXIX. Radical mono- and dideoxygenations with silanes
  作者：Derek H.R. Barton、Doo Ok Jang、Joseph Cs. Jaszberenyi

  DOI：10.1016/s0040-4020(01)80380-x

  日期：1993.4

  Thionocarbonates and xanthates of primary and secondary alcohols, as well as bis-xanthates of vic-diols are readily deoxygenated to the corresponding hydrocarbons or olefins with phenylsilane, triphenylsilane, and triethylsilane in good yield.
• Radical mono- and dideoxygenations with the triethylsilane + benzoyl peroxide system.
  作者：Derek H.R. Barton、Doo Ok Jang、Joseph Cs. Jaszberenyi

  DOI：10.1016/0040-4039(91)80472-i

  日期：1991.12

  Thionocarbonates and xanthates of primary and secondary alcohols, as well as dixanthates of vic-diols can easily be deoxygenated to the corresponding hydrocarbons or olefins with triethylsilane and benzoyl peroxide in high-yielding radical reactions.
• The invention of radical reactions. Part 32. Radical deoxygenations, dehalogenations, and deaminations with dialkyl phosphites and hypophosphorous acid as hydrogen sources
  作者：Derek H. R. Barton、Doo Ok Jang、Joseph C. Jaszberenyi

  DOI：10.1021/jo00076a054

  日期：1993.11

  Reagents, containing a P-H bond, such as dimethyl phosphite, diethyl phosphite, hypophosphorous acid and various salts of hypophosphorous acid are effective radical reducing agents for organic halides, thionoesters, and isocyanides affording high yields of the corresponding hydrocarbons. Reduction of tertiary phenyl selenides and tertiary nitro compounds are not efficient under these conditions. Olefination of 1,2-diols is also accomplished via the corresponding thiocarbonyl derivatives using hypophosphorous acid and triethylamine in the presence of a suitable ''sacrificial olefin'' in moderate to good yields.