(2S,4R,5S)-4-O-t-butyldimethylsilyl-1,2-O-isopropylidene-1,2,4,5-tetrahydroxy-5-phenylpentan-3-one | 220820-69-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (2S,4R,5S)-4-O-t-butyldimethylsilyl-1,2-O-isopropylidene-1,2,4,5-tetrahydroxy-5-phenylpentan-3-one
• 英文别名: (2R,3S)-2-[tert-butyl(dimethyl)silyl]oxy-1-[(4S)-2,2-dimethyl-1,3-dioxolan-4-yl]-3-hydroxy-3-phenylpropan-1-one
• CAS: 220820-69-9
• 化学式: C₂₀H₃₂O₅Si
• 分子量: 380.557
• InChiKey: NNLUSVIANJSKAC-XYJFISCASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.83
• 重原子数：
  26
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  65
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (2S,4R,5S)-4-O-t-butyldimethylsilyl-1,2-O-isopropylidene-1,2,4,5-tetrahydroxy-5-phenylpentan-3-one 在 4-二甲氨基吡啶 、 锂硼氢 、 4-甲基苯磺酸吡啶 、 三乙胺 、 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 二氯甲烷 、 水 为溶剂， 反应 100.0h， 生成
  参考文献：
  名称：

  Erythrulose derivatives as functionalized chiral d3 and d4 synthons

  摘要：

  Protected erythrulose derivatives have been shown to undergo highly stereoselective dicyclohexylboron chloride-mediated aldol reactions. After suitable synthetic manipulation of the resulting aldol adducts, chiral polyoxygenated molecules can be obtained in which either three or all four carbon atoms of the starting erythrulose molecule have been incorporated. Erythrulose derivatives may therefore behave, according to convenience, as chiral, functionalized d(3) or d(4) synthons. As an example, this methodology has been applied to a stereoselective synthesis of the naturally occurring, pharmacologically active lactone (+)-boronolide. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(02)00638-9
• 作为产物：
  描述：

  2-[tert-butyl(dimethyl)silyl]oxy-1-[(4S)-2,2-dimethyl-1,3-dioxolan-4-yl]ethanone 、 苯甲醛 在 氯代二环己基硼烷 、 三乙胺 作用下， 以 乙醚 为溶剂， 反应 4.0h， 生成 (2S,4R,5S)-4-O-t-butyldimethylsilyl-1,2-O-isopropylidene-1,2,4,5-tetrahydroxy-5-phenylpentan-3-one
  参考文献：
  名称：

  保护基对带有赤藓糖衍生物的硼醇醛加成物的顺/反立体选择性的影响。理论和实验研究

  摘要：

  我们已经研究了由二环己基氯化硼介导的一系列受保护的1-赤藓糖衍生物的羟醛加成物。的顺式/反立体选择性已发现取决于保护的羟基基团的功能，在C-3和C-4的类型。因此，在相同的反应条件下，在这些羟基上被苄基化的赤藓糖仅产生顺式羟醛，而相应的苯甲酰化衍生物则给出了反式羟醛。烯醇化物的手性居民促进了完整的内部1,3-诱导，这是顺式中两个醛醇的类型。在理论计算和实验数据的支持下，提出了机械建议。

  DOI：

  10.1016/s0040-4020(02)01279-6

文献信息

• Boron aldol additions with erythrulose derivatives: dependence of stereoselectivity on the type of protecting group
  作者：Miguel Carda、Eva Falomir、Juan Murga、Encarnación Castillo、Florenci González、J. Alberto Marco

  DOI：10.1016/s0040-4039(99)01380-5

  日期：1999.9

  Boron aldol additions of 1-O-silylated 3,4-di-O-benzyl- and 3,4-di-O-benzoyl-l-erythrulose and achiral aldehydes using dicyclohexylboron chloride have been investigated. The dibenzyl derivative gave syn/syn stereoisomers with high stereoselectivity, whereas the dibenzoyl derivative gave syn/anti stereoisomers. It is believed that, while the dibenzoyl erythrulose gives rise to the E enolate in the presence

  已经研究了使用二环己基氯化硼对1 - O-甲硅烷基化的3，4-二-O-苄基-和3，4-二-O-苯甲酰基-1-赤藓糖和非手性醛的硼醇醛加成。二苄基衍生物给出了具有高立体选择性的顺式/顺式立体异构体，而二苯甲酰基衍生物给出了顺式/反式立体异构体。据信，虽然二苯甲酰赤藓酮糖产生了È烯醇化物中的dicyclohexylboron酰氯存在，因为通常与该试剂观察到，只有ž形成在二苄基衍生物的情况下的烯醇化物。
• Aldol Reactions with Erythrulose Derivatives: Stereoselective Synthesis of Differentially Protected syn -α,β-Dihydroxy Esters
  作者：M. Carda、J. Murga、E. Falomir、F. González、J.A. Marco

  DOI：10.1016/s0040-4020(99)01041-8

  日期：2000.1

  Boron enolates of 1-O-silylated erythrulose 3,4-acetonides prepared with Brown's chloro-dicyclohexylborane/tertiary amine system have been shown to react with achiral aldehydes in a highly stereoselective way to yield a 1,2-syn/1,3-syn stereoisomer. Through oxidative cleavage of the aldol adducts with periodic acid hydrate, enantiopure syn-alpha,beta-dihydroxy esters with either hydroxyl group differently protected have been prepared. These erythrulose derivatives therefore behave as a chiral hydroxy acetate (glycolate) enolate equivalent. (C) 2000 Elsevier Science Ltd. All rights reserved.
• Erythrulose as a multifunctional chiron: Highly stereoselective boron aldol additions
  作者：J.Alberto Marco、Miguel Carda、Eva Falomir、Claudio Palomo、Mikel Oiarbide、J.Aurelio Ortiz、Anthony Linden

  DOI：10.1016/s0040-4039(99)80113-0

  日期：1999.1

  We have investigated the formation of various metal enolates of 1-O-silylated erythrulose 3,4-acetonides. We were able to prepare boron enolates using Brown's dicyclohexylboron chloride/tertiary amine system. When these enolates were allowed to react with a range of achiral aldehydes, highly stereoselective aldol additions took place with formation of the syn/syn stereoisomer. This has been attributed to the exclusive formation of a Z boron enolate, which is in a sharp contrast with the usual behaviour of the aforementioned reagent. (C) 1999 Elsevier Science Ltd. All rights reserved.
• Erythrulose derivatives as functionalized chiral d3 and d4 synthons
  作者：Juan Murga、Eva Falomir、Miguel Carda、J.Alberto Marco

  DOI：10.1016/s0957-4166(02)00638-9

  日期：2002.10

  Protected erythrulose derivatives have been shown to undergo highly stereoselective dicyclohexylboron chloride-mediated aldol reactions. After suitable synthetic manipulation of the resulting aldol adducts, chiral polyoxygenated molecules can be obtained in which either three or all four carbon atoms of the starting erythrulose molecule have been incorporated. Erythrulose derivatives may therefore behave, according to convenience, as chiral, functionalized d(3) or d(4) synthons. As an example, this methodology has been applied to a stereoselective synthesis of the naturally occurring, pharmacologically active lactone (+)-boronolide. (C) 2002 Elsevier Science Ltd. All rights reserved.
• Influence of the protecting groups on the syn/anti stereoselectivity of boron aldol additions with erythrulose derivatives. A theoretical and experimental study
  作者：Juan Murga、Eva Falomir、Florenci González、Miguel Carda、J.A Marco

  DOI：10.1016/s0040-4020(02)01279-6

  日期：2002.11

  of protected l-erythrulose derivatives mediated by dicyclohexyl boron chloride. The syn/anti stereoselectivity has been found to depend on the type of protecting groups on the hydroxyl functions at C-3 and C-4. Thus, erythruloses benzylated at these hydroxyl groups gave only syn aldols while the corresponding benzoylated derivatives gave anti aldols under the same reaction conditions. The resident chirality

  我们已经研究了由二环己基氯化硼介导的一系列受保护的1-赤藓糖衍生物的羟醛加成物。的顺式/反立体选择性已发现取决于保护的羟基基团的功能，在C-3和C-4的类型。因此，在相同的反应条件下，在这些羟基上被苄基化的赤藓糖仅产生顺式羟醛，而相应的苯甲酰化衍生物则给出了反式羟醛。烯醇化物的手性居民促进了完整的内部1,3-诱导，这是顺式中两个醛醇的类型。在理论计算和实验数据的支持下，提出了机械建议。