(3aS,4S,6aR)-4-[[tert-butyl(diphenyl)silyl]oxymethyl]-3,3a,4,6a-tetrahydrofuro[3,4-c]pyrazol-6-one | 106820-48-8

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (3aS,4S,6aR)-4-[[tert-butyl(diphenyl)silyl]oxymethyl]-3,3a,4,6a-tetrahydrofuro[3,4-c]pyrazol-6-one
• CAS: 106820-48-8
• 化学式: C₂₂H₂₆N₂O₃Si
• 分子量: 394.546
• InChiKey: FQESPLQIERDWGH-VAMGGRTRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.94
• 重原子数：
  28
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  60.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (3aS,4S,6aR)-4-[[tert-butyl(diphenyl)silyl]oxymethyl]-3,3a,4,6a-tetrahydrofuro[3,4-c]pyrazol-6-one 在 Rh/Al₂O₃ MoO5*pyridine*HMPA 、 氢气 、 双(三甲基硅烷基)氨基钾 、 calcium carbonate 作用下， 以 乙酸乙酯 、 甲苯 为溶剂， -78.0~-55.0 ℃ 、344.73 kPa 条件下， 反应 5.0h， 生成 (2R,3R,4S)-5-[(tert-butyldiphenylsilyl)oxy]-2-hydroxy-3-methyl-4-pentanolide
  参考文献：
  名称：

  立体化学控制自然界的生物合成途径：从单个手性祖细胞合成0f聚丙烯酸酯衍生的结构单元的一般策略

  摘要：

  提出了允许立体控制构造包含邻位和/或交替的烷基和羟基取代基的无环链的一般策略。从常见的手性中间体合成了离子霉素的结构亚基。

  DOI：

  10.1016/s0040-4020(01)87683-3
• 作为产物：
  描述：

  (5S)-5-(hydroxymethyl)-5H-furan-2-one 在 4-二甲氨基吡啶 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 18.0h， 生成 (3aS,4S,6aR)-4-[[tert-butyl(diphenyl)silyl]oxymethyl]-3,3a,4,6a-tetrahydrofuro[3,4-c]pyrazol-6-one
  参考文献：
  名称：

  Controlling π-Facial Diastereoselectivity in the 1,3-Dipolar Cycloadditions of Diazomethane to Chiral Pentenoates and Furanones:  Enantioselective Stereodivergent Syntheses of Cyclopropane Hydroxy Acids and Didehydro Amino Acids

  摘要：

  The title compounds have been synthesized in both enantiomeric forms and in good overall yields by using D-glyceraldehyde as the single chiral precursor. The efficiency and usefulness of the synthetic routes have been secured by performing controlled manipulations of the functional groups and by highly stereoselective transformations, namely Wittig-Horner condensations and cyclopropanations. Cyclopropane derivatives have been synthesized through 1,3-dipolar cycloaddition of diazomethane to chiral pentenoates or furanones obtained, in turn, from D-glyceraldehyde. Syn/anti stereochemistry of the cycloadducts has been unequivocally assigned and rationalized. Since pi-facial diastereoselectivity involved in these cycloadditions is the opposite for cyclic and open-chain structures, enantiomeric series of products can be derived.

  DOI：

  10.1021/jo972219a

文献信息

• Stereochemical control of nature's biosynthetic pathways:A general strategy for the synthesis 0f polypropionate-derived structural units from a single chiral progenitor
  作者：S. Hanessian、P.J. Murray

  DOI：10.1016/s0040-4020(01)87683-3

  日期：1987.1

  A general strategy that permits the stereocontrolled construction of acyclic chains containing vicinal and/or alternating alkyl and hydroxy substitutents is presented. Structural subunits of ionomycin were synthesized from a common chiral intermediate.

  提出了允许立体控制构造包含邻位和/或交替的烷基和羟基取代基的无环链的一般策略。从常见的手性中间体合成了离子霉素的结构亚基。
• Stereoselective synthesis of enantiopure cyclopropane didehydroamino acid derivatives: (−)-(Z)-2-Benzyloxycarbonylamino-4,5-cyclopropane-2-hexenodioic acid dimethyl ester
  作者：Neuh Hanafi、Rosa M. Ortuño

  DOI：10.1016/0957-4166(94)80074-x

  日期：1994.9

  The title amino acid derivative has been synthesized stereoselectively in 40% overall yield from 5-tert-butyldiphenylsilyloxymethyl-2(5H)-furanone used as a chiral precursor.
• A versatile protocol for the stereocontrolled elaboration of vicinal secondary and tertiary centers of relevance to natural product synthesis
  作者：Stephen Hanessian、Peter J. Murray

  DOI：10.1021/jo00382a043

  日期：1987.3
• Controlling π-Facial Diastereoselectivity in the 1,3-Dipolar Cycloadditions of Diazomethane to Chiral Pentenoates and Furanones:  Enantioselective Stereodivergent Syntheses of Cyclopropane Hydroxy Acids and Didehydro Amino Acids
  作者：Marta Martín-Vilà、Neuh Hanafi、José M. Jiménez、Angel Alvarez-Larena、Joan F. Piniella、Vicenç Branchadell、Antonio Oliva、Rosa M. Ortuño

  DOI：10.1021/jo972219a

  日期：1998.5.1

  The title compounds have been synthesized in both enantiomeric forms and in good overall yields by using D-glyceraldehyde as the single chiral precursor. The efficiency and usefulness of the synthetic routes have been secured by performing controlled manipulations of the functional groups and by highly stereoselective transformations, namely Wittig-Horner condensations and cyclopropanations. Cyclopropane derivatives have been synthesized through 1,3-dipolar cycloaddition of diazomethane to chiral pentenoates or furanones obtained, in turn, from D-glyceraldehyde. Syn/anti stereochemistry of the cycloadducts has been unequivocally assigned and rationalized. Since pi-facial diastereoselectivity involved in these cycloadditions is the opposite for cyclic and open-chain structures, enantiomeric series of products can be derived.