1,5-anhydro-4,6-di-O-benzyl-2,3-dideoxy-3-diphenylphosphoryl-D-ribo-hex-1-enitol | 639499-36-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1,5-anhydro-4,6-di-O-benzyl-2,3-dideoxy-3-diphenylphosphoryl-D-ribo-hex-1-enitol
• 英文别名: (2R,3R,4S)-4-diphenylphosphoryl-3-phenylmethoxy-2-(phenylmethoxymethyl)-3,4-dihydro-2H-pyran
• CAS: 639499-36-8
• 化学式: C₃₂H₃₁O₄P
• 分子量: 510.569
• InChiKey: XFMITLKZMKRORL-YKILCQELSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.5
• 重原子数：
  37
• 可旋转键数：
  10
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.19
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1,5-anhydro-4,6-di-O-benzyl-2,3-dideoxy-3-diphenylphosphoryl-D-ribo-hex-1-enitol 在 palladium on activated charcoal 咪唑 、 氢气 作用下， 以 四氢呋喃 、 乙二醇二甲醚 、 乙醇 为溶剂， 20.0 ℃ 、455.96 kPa 条件下， 反应 86.0h， 生成 1,5-anhydro-2,3-dideoxy-6-O-tert-butyldimethylsilyl-3-diphenylphosphinoyl-D-ribo-hexitol
  参考文献：
  名称：

  Regioselective Synthesis of Phosphonylated Sugars from Reactions of Glycals with Diphenylphosphenium Cation

  摘要：

  Reaction of methyl 4,6-di-O-acetyl-2,3-dideoxy-D-erythro-hex-2-enopyranoside 1 with two equivalents of diphertylphosphenium cation at 0degreesC gave the 1-phosphonylated 2-enopyranos ides 3alpha and 3beta as major products. Similarly, reaction of diphenylphosphenium cation with tri-O-acetylglycal afforded the same products in a similar ratio. In contrast, a reaction with tri-O-benzylglucal at reflux temperature of dichloromethane afforded the 3-phosphonylated sugar 13 as a major product. These reactions may proceed via stable allyl cations.

  DOI：

  10.1081/car-120025330
• 作为产物：
  描述：

  3,4,6-三苄氧基-D-葡萄烯糖 、 二苯基氯化膦 在 aluminum (III) chloride 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 以49%的产率得到1,5-anhydro-4,6-di-O-benzyl-2,3-dideoxy-3-diphenylphosphoryl-D-ribo-hex-1-enitol
  参考文献：
  名称：

  通过碳水化合物端基的烷氧基自由基的裂解合成手性β-碘-和乙烯基有机磷（V）化合物

  摘要：

  使用异头烷氧基自由基裂解反应作为关键步骤，已开发出一种合成手性乙烯基膦酸酯和乙烯基膦氧化物碳水化合物衍生物的新通用方法。合成序列通过β-碘膦酸酯和β-碘膦氧化物中间体进行，这可能是将磷引入有机分子的有趣合成子。这些乙烯基膦酸酯可以容易地转化成2-亚甲基-1-磷酸戊呋喃糖酶（3-亚甲基-1,2-氧代膦酸酯）和β-氨基膦酸酯，分别是具有生物活性的α-亚甲基-γ-内酯和β-氨基酸的等排体。

  DOI：

  10.1021/ol302939z

文献信息

• Fragmentation of Carbohydrate Anomeric Alkoxyl Radicals: Synthesis of Chiral Polyhydroxylated β-Iodo- and Alkenylorganophosphorus(V) Compounds
  作者：Daniel Hernández-Guerra、María S. Rodríguez、Ernesto Suárez

  DOI：10.1002/ejoc.201402387

  日期：2014.8

  A direct approach to β-iodophosphonates and β-iodophosphine oxides from 2,3-dideoxy-3-phosphoryl carbohydrate derivatives has been achieved by using the anomeric alkoxyl radical 1,2-fragmentation protocol. The reaction has been conducted on carbohydrate derivatives under mild conditions with (diacetoxyiodo)benzene and molecular iodine. Subsequent dehydroiodination afforded the corresponding vinylphosphonates

  通过使用异头烷氧基自由基 1,2-片段化方案，已经实现了从 2,3-dideoxy-3-phosphoryl 碳水化合物衍生物直接制备 β-iodophosphonates 和 β-iodophosphine 氧化物的方法。该反应是在温和条件下与（二乙酰氧基碘）苯和分子碘对碳水化合物衍生物进行的。随后脱氢碘化得到相应的乙烯基膦酸酯和乙烯基氧化膦。
• Synthesis of Chiral β-Iodo- and Vinylorganophosphorus(V) Compounds by Fragmentation of Carbohydrate Anomeric Alkoxyl Radicals
  作者：Daniel Hernández-Guerra、María S. Rodríguez、Ernesto Suárez

  DOI：10.1021/ol302939z

  日期：2013.1.18

  synthesis of chiral vinylphosphonate and vinylphosphine oxide carbohydrate derivatives has been developed using the anomeric alkoxyl radical fragmentation reaction as the key step. The synthetic sequence proceeded via β-iodophosphonate and β-iodophosphine oxide intermediates, which may be interesting synthons for the introduction of phosphorus into organic molecules. These vinylphosphonates could be easily

  使用异头烷氧基自由基裂解反应作为关键步骤，已开发出一种合成手性乙烯基膦酸酯和乙烯基膦氧化物碳水化合物衍生物的新通用方法。合成序列通过β-碘膦酸酯和β-碘膦氧化物中间体进行，这可能是将磷引入有机分子的有趣合成子。这些乙烯基膦酸酯可以容易地转化成2-亚甲基-1-磷酸戊呋喃糖酶（3-亚甲基-1,2-氧代膦酸酯）和β-氨基膦酸酯，分别是具有生物活性的α-亚甲基-γ-内酯和β-氨基酸的等排体。
• Regioselective Synthesis of Phosphonylated Sugars from Reactions of Glycals with Diphenylphosphenium Cation
  作者：Akira Takano、Hiroyuki Fukuhara、Tadao Ohno、Masahiro Kutsuma、Tetsuya Fujimoto、Hirofusa Shirai、Ryozo Iriye、Akikazu Kakehi、Iwao Yamamoto

  DOI：10.1081/car-120025330

  日期：2003.1.10

  Reaction of methyl 4,6-di-O-acetyl-2,3-dideoxy-D-erythro-hex-2-enopyranoside 1 with two equivalents of diphertylphosphenium cation at 0degreesC gave the 1-phosphonylated 2-enopyranos ides 3alpha and 3beta as major products. Similarly, reaction of diphenylphosphenium cation with tri-O-acetylglycal afforded the same products in a similar ratio. In contrast, a reaction with tri-O-benzylglucal at reflux temperature of dichloromethane afforded the 3-phosphonylated sugar 13 as a major product. These reactions may proceed via stable allyl cations.