(2R,3S)-1-benzyl-3-tert-butyldimethylsilyloxy-2-hydroxymethylpyrrolidine | 156045-81-7

• 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: (2R,3S)-1-benzyl-3-tert-butyldimethylsilyloxy-2-hydroxymethylpyrrolidine
• 英文别名: [(2R,3S)-1-benzyl-3-[tert-butyl(dimethyl)silyl]oxypyrrolidin-2-yl]methanol
• CAS: 156045-81-7
• 化学式: C₁₈H₃₁NO₂Si
• 分子量: 321.535
• InChiKey: PPCMHJUKOBNNDA-SJORKVTESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.64
• 重原子数：
  22
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  32.7
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (2R,3S)-1-benzyl-3-tert-butyldimethylsilyloxy-2-hydroxymethylpyrrolidine 在 palladium on activated charcoal 盐酸 、 ruthenium trichloride 、 sodium periodate 、 氢气 作用下， 以 甲醇 、 四氯化碳 、 水 、 乙腈 为溶剂， 25.0 ℃ 、2.0 MPa 条件下， 反应 7.5h， 生成 反-3-羟基-L-脯氨酸
  参考文献：
  名称：

  Chiral pool synthesis of trans-(2S3S)-3-hydroxyproline and castanodiol from S-pyroglutamic acid.

  摘要：

  The Pyroglutamic acid derivative 1 was converted through several steps into Castanodiol 9 and 2S,3S-3-Hydroxyproline 11. Key steps of the reaction sequence were the stereoselective epoxidation of 1 to 2 and the regioselective ring opening of 2 to 3. BH3.S(CH3)(2) reduction of the amide group of 3 and 4 resulted in a concomitant transformation of the acetal moiety into the N-benzyl protecting group. The air sensitive 5 and 6, were transformed to the stable N-Boc prolinol derivatives 7 and 8. Deprotection of 8 provided 9, while oxidation of 8 gave the protected proline derivative 10. Deprotection of 10 furnished enantiopure 2S,3S-3-Hydroxyproline 11.

  DOI：

  10.1016/s0957-4166(00)80492-9
• 作为产物：
  描述：

  (3R,7aS)-3-phenyl-6-(phenylselanyl)tetrahydro-3H,5H-pyrrolo[1,2-c]oxazol-5-one 在 咪唑 、 叔丁基过氧化氢 、 四甲基乙二胺 、 aluminium amalgam 、 dimethyl sulfide borane 、 四丁基氟化铵 、 双氧水 、 碳酸氢钠 、 potassium carbonate 作用下， 以 四氢呋喃 、 异辛烷 、 乙醇 、 乙酸乙酯 、 N,N-二甲基甲酰胺 、 丙酮 为溶剂， 反应 18.67h， 生成 (2R,3S)-1-benzyl-3-tert-butyldimethylsilyloxy-2-hydroxymethylpyrrolidine
  参考文献：
  名称：

  Chiral pool synthesis of trans-(2S3S)-3-hydroxyproline and castanodiol from S-pyroglutamic acid.

  摘要：

  The Pyroglutamic acid derivative 1 was converted through several steps into Castanodiol 9 and 2S,3S-3-Hydroxyproline 11. Key steps of the reaction sequence were the stereoselective epoxidation of 1 to 2 and the regioselective ring opening of 2 to 3. BH3.S(CH3)(2) reduction of the amide group of 3 and 4 resulted in a concomitant transformation of the acetal moiety into the N-benzyl protecting group. The air sensitive 5 and 6, were transformed to the stable N-Boc prolinol derivatives 7 and 8. Deprotection of 8 provided 9, while oxidation of 8 gave the protected proline derivative 10. Deprotection of 10 furnished enantiopure 2S,3S-3-Hydroxyproline 11.

  DOI：

  10.1016/s0957-4166(00)80492-9

文献信息

• Access to Optically Active 3-Aminopiperidines by Ring Expansion of Prolinols: Thermodynamic versus Kinetic Control
  作者：Anne Cochi、Domingo Gomez Pardo、Janine Cossy

  DOI：10.1002/ejoc.201101829

  日期：2012.4

  3-Aminopiperidines are of great interest because they can possess a wide range of biological activity depending on the nitrogen substituents. Different approaches their synthesis are presented and the most efficient is a ring expansion of prolinols induced by XtalFluor-E (diethylaminodifluorosulfinium tetrafluoroborate) in the presence of tetrabutylammonium azide, via an aziridinium intermediate, followed

  3-氨基哌啶很受关注，因为它们可以根据氮取代基而具有广泛的生物活性。提出了不同的合成方法，最有效的是在四丁基叠氮化铵的存在下，通过氮丙啶中间体，由 XtalFluor-E（二乙基氨基二氟锍四氟硼酸盐）诱导的脯氨醇扩环，然后还原相应的叠氮化物。在动力学条件下，取决于脯氨醇上存在的取代基，可以获得 0:100 的 2-（叠氮甲基）吡咯烷/3-叠氮哌啶比率。
• Ring Expansion Induced by DAST: Synthesis of Substituted 3-Fluoropiperidines from Prolinols and 3-Fluoroazepanes from 2-Hydroxymethylpiperidines
  作者：Ingrid Déchamps、Domingo Gomez Pardo、Janine Cossy

  DOI：10.1002/ejoc.200700237

  日期：2007.9

  Optically active prolinols can be converted into optically active 3-fluoropiperidines by treatment with DAST. The reaction often produces 2-fluoromethylpyrrolidines as byproducts. The ring expansion was also applied to 2-hydroxypiperidines to produce 3-fluoroazepanes. The rearrangement proceeds via an aziridinium intermediate. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

  光学活性脯氨醇可以通过 DAST 处理转化为光学活性 3-氟哌啶。该反应通常会产生 2-氟甲基吡咯烷作为副产物。扩环也适用于 2-羟基哌啶以产生 3-氟氮杂环庚烷。重排通过氮丙啶中间体进行。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)
• Chiral pool synthesis of trans-(2S3S)-3-hydroxyproline and castanodiol from S-pyroglutamic acid.
  作者：Claus Herdeis、Hans Peter Hubmann、Hermann Lotter

  DOI：10.1016/s0957-4166(00)80492-9

  日期：1994.1

  The Pyroglutamic acid derivative 1 was converted through several steps into Castanodiol 9 and 2S,3S-3-Hydroxyproline 11. Key steps of the reaction sequence were the stereoselective epoxidation of 1 to 2 and the regioselective ring opening of 2 to 3. BH3.S(CH3)(2) reduction of the amide group of 3 and 4 resulted in a concomitant transformation of the acetal moiety into the N-benzyl protecting group. The air sensitive 5 and 6, were transformed to the stable N-Boc prolinol derivatives 7 and 8. Deprotection of 8 provided 9, while oxidation of 8 gave the protected proline derivative 10. Deprotection of 10 furnished enantiopure 2S,3S-3-Hydroxyproline 11.

表征谱图