(S,S)-2-(2-hydroxy-2-phenyl-ethyl)-piperidine-1-carboxylic acid tert-butyl ester | 639458-44-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 哌啶类
• 英文名称: (S,S)-2-(2-hydroxy-2-phenyl-ethyl)-piperidine-1-carboxylic acid tert-butyl ester
• 英文别名: tert-butyl (2S)-2-[(2S)-2-hydroxy-2-phenylethyl]piperidine-1-carboxylate；tert-butyl (S)-2-[(S)-2-hydroxy-2-phenylethyl]piperidine-1-carboxylate；(S)-tert-butyl 2[(S)-2-hydroxy-2-phenylethyl]piperidine-1-carboxylate
• CAS: 639458-44-9
• 化学式: C₁₈H₂₇NO₃
• 分子量: 305.417
• InChiKey: JJSHQEUQYFNZAY-HOTGVXAUSA-N

物化性质

• 熔点：
  58-59 °C
• 沸点：
  424.9±18.0 °C(Predicted)
• 密度：
  1.085±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  22
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.61
• 拓扑面积：
  49.8
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (S,S)-2-(2-hydroxy-2-phenyl-ethyl)-piperidine-1-carboxylic acid tert-butyl ester 在 盐酸 作用下， 以 1,4-二氧六环 、 乙腈 为溶剂， 反应 0.25h， 以98%的产率得到景天定
  参考文献：
  名称：

  使用流动化学技术合成（+）-Dumetorine和同类物

  摘要：

  描述了使用流技术有效合成天然生物碱（+）-硬脂碱的方法。该工艺从对映体（S）-2-（哌啶-2--2-基）乙醇4开始需要五个单独的步骤4总收率为29％。大多数反应是通过利用溶剂过热和使用固定化试剂或清除剂的填充柱来进行的，以最大程度地减少处理。公开了在连续流动下进行经典反应的新方案：使用新型聚乙二醇负载的Hoveyda催化剂进行的开环复分解反应和空前的流动脱保护/ Eschweiler-Clarke甲基化序列。为合成（+）-杜美汀开发的新方案被应用到其简化的天然同源物（-）-sedamine和（+）-sedridine的合成中。

  DOI：

  10.1002/chem.201100300
• 作为产物：
  描述：

  (R)-2-(2-acetoxy-ethyl)-piperidine-1-carboxylic acid tert-butyl ester 在 草酰氯 、 sodium carbonate 、 二甲基亚砜 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 反应 4.0h， 生成 (S,S)-2-(2-hydroxy-2-phenyl-ethyl)-piperidine-1-carboxylic acid tert-butyl ester
  参考文献：
  名称：

  Remote Stereocenter Discrimination in the Enzymatic Resolution of Piperidine-2-ethanol. Short Enantioselective Synthesis of Sedamine and Allosedamine

  摘要：

  Kinetic resolution of N-Boc-piperidine-2-ethanol (2), a case of remote stereocenter discrimination, was accomplished by sequential transesterification mediated by two enzymes, Lipase PS and porcine pancreatic lipase, showing opposite enantioselectivity. The gram-scale availability of the two enantiomeric N-Boc alcohols 2a (R) and 2c (S) enlarges their synthetic exploitation for the enantioselective preparation of piperidine alkaloids. As an example, the convenient three-step synthesis of both the enantiomers of sedamine and allosedamine is described.

  DOI：

  10.1021/jo035215g

文献信息

• Pd-Catalyzed Enantioselective Aerobic Oxidation of Secondary Alcohols: Applications to the Total Synthesis of Alkaloids
  作者：Shyam Krishnan、Jeffrey T. Bagdanoff、David C. Ebner、Yeeman K. Ramtohul、Uttam K. Tambar、Brian M. Stoltz

  DOI：10.1021/ja804738b

  日期：2008.10.15

  Enantioselective syntheses of the alkaloids (-)-aurantioclavine, (+)-amurensinine, (-)-lobeline, and (-)- and (+)-sedamine are described. The syntheses demonstrate the effectiveness of the Pd-catalyzed asymmetric oxidation of secondary alcohols in diverse contexts and the ability of this methodology to set the absolute configuration of multiple stereocenters in a single operation. The utility of an

  描述了生物碱 (-)-aurantioclavine、(+)-amurensinine、(-)-lobeline 和 (-)- 和 (+)-sedamine 的对映选择性合成。合成证明了 Pd 催化的仲醇不对称氧化在不同环境中的有效性，以及该方法在单个操作中设置多个立体中心的绝对构型的能力。还描述了芳烃 CC 插入反应在访问复杂多环框架中的效用。
• Enantioselective Synthesis of (+)-α-Conhydrine and (-)-Sedamine by L-Proline-Catalysed α-Aminooxylation
  作者：Tanveer Mahamadali Shaikh、Arumugam Sudalai

  DOI：10.1002/ejoc.201000169

  日期：——

  An efficient organocatalytic approach to the enantioslective synthesis of two important piperidine alkaloids, namely (+)-α-conhydrine (98 % ee) and (-)-sedamine (95 % ee), by L -proline-catalysed α-aminooxylation of aldehydes has been developed. The strategy involves an intramolecular cyclization to construct the piperidine core.

  一种有效的有机催化方法，通过 L-脯氨酸催化的醛的 α-氨基氧基化，对映选择性合成两种重要的哌啶生物碱，即 (+)-α-conhydrine (98% ee) 和 (-)-sedamine (95% ee)已经被开发出来。该策略涉及分子内环化以构建哌啶核心。
• Kinetic Resolution of Secondary Alcohols Using Amidine-Based Catalysts
  作者：Ximin Li、Hui Jiang、Eric W. Uffman、Lei Guo、Yuhua Zhang、Xing Yang、Vladimir B. Birman

  DOI：10.1021/jo202220x

  日期：2012.2.17

  Kinetic resolution of racemic alcohols has been traditionally achieved via enzymatic enantioselective esterification and ester hydrolysis. However, there has long been considerable interest in devising nonenzymatic alternative methods for this transformation. Amidine-based catalysts (ABCs), a new class of enantioselective acyl transfer catalysts developed in our group, have demonstrated, inter alia, high efficacy in the kinetic resolution of benzylic, allylic, and propargylic secondary alcohols and 2-substituted cycloalkanols, and thus provide a viable alternative to enzymes.
• Synthesis of (+)‐Dumetorine and Congeners by Using Flow Chemistry Technologies
  作者：Elena Riva、Anna Rencurosi、Stefania Gagliardi、Daniele Passarella、Marisa Martinelli

  DOI：10.1002/chem.201100300

  日期：2011.5.23

  protocols for performing classical reactions under continuous flow are disclosed: the ring‐closing metathesis reaction with a novel polyethylene glycol‐supported Hoveyda catalyst and the unprecedented flow deprotection/Eschweiler–Clarke methylation sequence. The new protocols developed for the synthesis of (+)‐dumetorine were applied to the synthesis of its simplified natural congeners (−)‐sedamine and (+)‐sedridine

  描述了使用流技术有效合成天然生物碱（+）-硬脂碱的方法。该工艺从对映体（S）-2-（哌啶-2--2-基）乙醇4开始需要五个单独的步骤4总收率为29％。大多数反应是通过利用溶剂过热和使用固定化试剂或清除剂的填充柱来进行的，以最大程度地减少处理。公开了在连续流动下进行经典反应的新方案：使用新型聚乙二醇负载的Hoveyda催化剂进行的开环复分解反应和空前的流动脱保护/ Eschweiler-Clarke甲基化序列。为合成（+）-杜美汀开发的新方案被应用到其简化的天然同源物（-）-sedamine和（+）-sedridine的合成中。
• Remote Stereocenter Discrimination in the Enzymatic Resolution of Piperidine-2-ethanol. Short Enantioselective Synthesis of Sedamine and Allosedamine
  作者：Marco Angoli、Alessio Barilli、Giordano Lesma、Daniele Passarella、Sergio Riva、Alessandra Silvani、Bruno Danieli

  DOI：10.1021/jo035215g

  日期：2003.11.1

  Kinetic resolution of N-Boc-piperidine-2-ethanol (2), a case of remote stereocenter discrimination, was accomplished by sequential transesterification mediated by two enzymes, Lipase PS and porcine pancreatic lipase, showing opposite enantioselectivity. The gram-scale availability of the two enantiomeric N-Boc alcohols 2a (R) and 2c (S) enlarges their synthetic exploitation for the enantioselective preparation of piperidine alkaloids. As an example, the convenient three-step synthesis of both the enantiomers of sedamine and allosedamine is described.