(5R,6S)-5-(tert-butyldimethylsilyloxy)-6-methylpiperidin-2-one | 908129-97-5

• 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: (5R,6S)-5-(tert-butyldimethylsilyloxy)-6-methylpiperidin-2-one
• 英文别名: (5R,6S)-5-[tert-butyl(dimethyl)silyl]oxy-6-methylpiperidin-2-one
• CAS: 908129-97-5
• 化学式: C₁₂H₂₅NO₂Si
• 分子量: 243.421
• InChiKey: VPWYVWJOAQVCPK-VHSXEESVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.68
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  38.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (5R,6S)-5-(tert-butyldimethylsilyloxy)-6-methylpiperidin-2-one 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 以76%的产率得到(5R,6S)-5-hydroxy-6-methylpiperidin-2-one
  参考文献：
  名称：

  Diastereoselective syntheses of 2-amino propargyl alcohols. Chiral building blocks for enantiopure amino γ-lactones and 5-hydroxy-piperidinone derivatives

  摘要：

  alpha-Dibenzylamino aldehydes, derived from the corresponding natural alpha-amino acids, react with metal acetylides to yield anti-amino propargyl alcohols in good yield and diastereomeric excess. syn Amino alcohols are prepared from the. anti diastereo-isomers and all of them are elaborated in few steps to enantiopure amino lactones and hydroxy-piperidin-2-ones. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2006.05.131
• 作为产物：
  描述：

  (4R,5S)-4-(tert-Butyl-dimethyl-silanyloxy)-5-dibenzylamino-hex-2-ynoic acid benzyl ester 在 palladium dihydroxide 氢气 、 4-吡咯烷基吡啶 、 N,N'-二环己基碳二亚胺 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 生成 (5R,6S)-5-(tert-butyldimethylsilyloxy)-6-methylpiperidin-2-one
  参考文献：
  名称：

  Diastereoselective syntheses of 2-amino propargyl alcohols. Chiral building blocks for enantiopure amino γ-lactones and 5-hydroxy-piperidinone derivatives

  摘要：

  alpha-Dibenzylamino aldehydes, derived from the corresponding natural alpha-amino acids, react with metal acetylides to yield anti-amino propargyl alcohols in good yield and diastereomeric excess. syn Amino alcohols are prepared from the. anti diastereo-isomers and all of them are elaborated in few steps to enantiopure amino lactones and hydroxy-piperidin-2-ones. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2006.05.131

文献信息

• Asymmetric Synthesis of the Cytotoxic Marine Natural Product (+)-Awajanomycin and Its C-11 Epimer
  作者：Rui Fu、Jian-Liang Ye、Xi-Jie Dai、Yuan-Ping Ruan、Pei-Qiang Huang

  DOI：10.1021/jo100744c

  日期：2010.6.18

  the use of (R)-18 as the chiral building block to construct the γ-lactone-δ-lactam core 3 and cross-olefin metathesis as the key reaction to couple the latter with the allylic alcohol segment (R- or S-4). The efficient construction of the core 3 was realized by taking advantage of the inherent multiple reactivities of the chiral building block (R)-18. A highly diastereoselective one-pot transformation

  描述了融合的阿瓦那霉素合成方法的全部细节，以及通过改进的13步方法对海洋天然产物（+）-阿瓦那霉素（1）及其C-11差向异构体38进行的首次总合成。合成策略的关键要素在于使用（R）-18作为手性结构单元来构建γ-内酯-δ-内酰胺核3和交叉烯烃复分解是将后者与烯丙基偶联的关键反应酒精部分（R-或S - 4）。高效建设核心3通过利用手性结构单元（R）-18固有的多重反应性来实现。以“一石四鸟”的方式实现了6到26的高度非对映选择性的一锅转换。另一方面，区段4的两个对映异构体的对映选择性合成已经通过另一种更有效的两步法进行。合成了阿瓦宗霉素（1）和11-表-阿瓦宗霉素38，其总产率分别为3.8％和3.6％。进行了量子化学计算以揭示化合物27的低反应活性对甲氧羰基化，并得到一个洞察中间体的青睐构象25 - 27。另外，由于烯丙醇部分4的均偶联而产生的副产物39的几何形状被修改为E，并且发现了异常的环丙烷化反应。
• A divergent approach for asymmetric syntheses of (+)-spicigerine, (+)-cassine and their 3-epimers
  作者：Pan Han、Chang-Mei Si、Zhuo-Ya Mao、Hai-Tong Li、Bang-Guo Wei、Zhen-Ting Du

  DOI：10.1016/j.tet.2015.12.057

  日期：2016.2

  An efficient approach for asymmetric synthesis of (+)-spicigerine, (+)-cassine and their 3-epimers has been developed through the intramolecular diastereoselective tandem addition/cyclisation process of alpha-chiral aldimine 9 with methylmagnesium bromide and the asymmetric addition of nucleophilic reagents to aminal 14. Moreover, the first asymmetric synthesis of (+)-spicigerine has been achieved in this manuscript. In this synthetic strategy, the asymmetric syntheses of (+)-spicigerine and (+)-cassine was achieved in a 14% overall yield and nine steps and an 18% overall yield and seven steps from cheap a chiral aldimine 9, respectively. (C) 2015 Elsevier Ltd. All rights reserved.
• Diastereoselective syntheses of 2-amino propargyl alcohols. Chiral building blocks for enantiopure amino γ-lactones and 5-hydroxy-piperidinone derivatives
  作者：José María Andrés、Rafael Pedrosa、Alfonso Pérez-Encabo

  DOI：10.1016/j.tetlet.2006.05.131

  日期：2006.7

  alpha-Dibenzylamino aldehydes, derived from the corresponding natural alpha-amino acids, react with metal acetylides to yield anti-amino propargyl alcohols in good yield and diastereomeric excess. syn Amino alcohols are prepared from the. anti diastereo-isomers and all of them are elaborated in few steps to enantiopure amino lactones and hydroxy-piperidin-2-ones. (c) 2006 Elsevier Ltd. All rights reserved.