(S,S)-2,6-bis[(tert-butyldimethylsilyloxy)methyl]piperidine | 169330-73-8

• 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)-2,6-bis[(tert-butyldimethylsilyloxy)methyl]piperidine
• 英文别名: tert-butyl-[[(2S,6S)-6-[[tert-butyl(dimethyl)silyl]oxymethyl]piperidin-2-yl]methoxy]-dimethylsilane
• CAS: 169330-73-8
• 化学式: C₁₉H₄₃NO₂Si₂
• 分子量: 373.727
• InChiKey: GVZJXDHVGVNEJO-IRXDYDNUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.54
• 重原子数：
  24
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  30.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (S,S)-2,6-bis[(tert-butyldimethylsilyloxy)methyl]piperidine 在 potassium carbonate 作用下， 以 四氢呋喃 、 乙腈 为溶剂， 反应 48.0h， 生成 N-(2,2-diphenyl-2-hydroxyethyl)-(S,S)-2,6-bis[(tert-butyldimethylsiloxy)methyl]piperidine
  参考文献：
  名称：

  手性C 2对称的2,3-二取代的氮丙啶和2,6-二取代的哌啶为手性配体，在二乙基锌与芳醛的加成反应中

  摘要：

  已经成功地合成了具有β-氨基醇部分的手性C 2对称的2，3-二取代的氮丙啶和2，6-二取代的哌啶，并已在二乙基锌与芳醛在己烷中的不对称加成反应中研究了它们的催化手性诱导性能。当使用N-（2,2-二苯基-2-羟乙基）-（S，S）-2,3-双（甲氧基甲基）氮丙啶11作为催化手性配体时，形成具有（S）-构型的仲醇高产率为86–92％，而对映体过量（ee's）为11–13％。但是，当N-（2,2-二苯基-2-羟乙基）-（R时，R）-2,6-二取代哌啶衍生物16和20在相同反应条件下用作手性配体，相应仲醇的ee分别为20–30和5％–6％，以及配置。提出了这种反演的合理机制。

  DOI：

  10.1016/s0957-4166(00)00479-1
• 作为产物：
  描述：

  1,6-庚二烯 在 咪唑 、 4-二甲氨基吡啶 、 palladium dihydroxide 、 AD-mix-α 、 氢气 、 三乙胺 作用下， 以 甲醇 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 、 叔丁醇 为溶剂， 反应 96.0h， 生成 (S,S)-2,6-bis[(tert-butyldimethylsilyloxy)methyl]piperidine
  参考文献：
  名称：

  Symmetry-Assisted Synthesis of C₂-Symmetric trans-α,α‘-Bis(hydroxymethyl)pyrrolidine and -piperidine Derivatives via Double Sharpless Asymmetric Dihydroxylation of α,ω-Terminal Dienes

  摘要：

  A new strategy has been developed for the synthesis of C-2-symmetric trans-alpha,alpha'-bis(hydroxymethyl)pyrrolidine and piperidine derivatives 1-3 starting from symmetric alpha,omega-terminal dienes 4-6. The double-asymmetric dihydroxylation (AD) reaction of 4-6 gave C-2-symmetric tetrols, which were converted in a four-step sequence to C-2-symmetric azacycloalkanes 17, 9, and 22, respectively. These azacycloalkanes were transformed into 1-3 in high enantiomeric excess (82% --> 98%ee). The double AD reaction proved to cause enantiomeric enhancement, even though the asymmetric induction for the first AD reaction is moderate. In addition, it was observed that the chromatography on silica gel of several C-2-symmetric azacycloalkanes (17, 20, and 22) of varying ee's resulted in marked enantiomeric fractionation.

  DOI：

  10.1021/jo971995f

文献信息

• New entry to C2 symmetric trans-2,6-bis(hydroxymethyl)-piperidine derivatives via the Sharpless asymmetric dihydroxylation
  作者：Hiroki Takahata、Shin-ichi Kouno、Takefumi Momose

  DOI：10.1016/0957-4166(95)00131-8

  日期：1995.5

  A new synthesis of both enantiomers of C2-symmetric trans-2,6-bis(hydroxymethyl)piperidine derivatives 1 by the use, as a key reaction, of the Sharpless asymmetric dihydroxylation of a symmetric diene 2 is presented.

  通过使用对称二烯2的Sharpless不对称二羟基化作为关键反应，提出了一种C 2对称反式-2,6-双（羟甲基）哌啶衍生物1对映体的新合成方法。
• Symmetry-Assisted Synthesis of <i>C</i>₂-Symmetric <i>trans</i>-α,α‘-Bis(hydroxymethyl)pyrrolidine and -piperidine Derivatives via Double Sharpless Asymmetric Dihydroxylation of α,ω-Terminal Dienes
  作者：Hiroki Takahata、Seiki Takahashi、Shin-ichi Kouno、Takefumi Momose

  DOI：10.1021/jo971995f

  日期：1998.4.1

  A new strategy has been developed for the synthesis of C-2-symmetric trans-alpha,alpha'-bis(hydroxymethyl)pyrrolidine and piperidine derivatives 1-3 starting from symmetric alpha,omega-terminal dienes 4-6. The double-asymmetric dihydroxylation (AD) reaction of 4-6 gave C-2-symmetric tetrols, which were converted in a four-step sequence to C-2-symmetric azacycloalkanes 17, 9, and 22, respectively. These azacycloalkanes were transformed into 1-3 in high enantiomeric excess (82% --> 98%ee). The double AD reaction proved to cause enantiomeric enhancement, even though the asymmetric induction for the first AD reaction is moderate. In addition, it was observed that the chromatography on silica gel of several C-2-symmetric azacycloalkanes (17, 20, and 22) of varying ee's resulted in marked enantiomeric fractionation.
• Chiral C 2 -symmetric 2,3-disubstituted aziridine and 2,6-disubstituted piperidine as chiral ligands in the addition reaction of diethylzinc with arylaldehydes
  作者：Min Shi、Jian-Kang Jiang、Yan-Shu Feng

  DOI：10.1016/s0957-4166(00)00479-1

  日期：2000.12

  Chiral C2-symmetric 2,3-disubstituted aziridines and 2,6-disubstituted piperidines having a β-amino alcohol moiety have been successfully synthesized and their catalytic chiral induction properties have been examined in the asymmetric addition reactions of diethylzinc with arylaldehydes in hexane. When N-(2,2-diphenyl-2-hydroxyethyl)-(S,S)-2,3-bis(methoxymethyl)aziridine 11 was used as a catalytic

  已经成功地合成了具有β-氨基醇部分的手性C 2对称的2，3-二取代的氮丙啶和2，6-二取代的哌啶，并已在二乙基锌与芳醛在己烷中的不对称加成反应中研究了它们的催化手性诱导性能。当使用N-（2,2-二苯基-2-羟乙基）-（S，S）-2,3-双（甲氧基甲基）氮丙啶11作为催化手性配体时，形成具有（S）-构型的仲醇高产率为86–92％，而对映体过量（ee's）为11–13％。但是，当N-（2,2-二苯基-2-羟乙基）-（R时，R）-2,6-二取代哌啶衍生物16和20在相同反应条件下用作手性配体，相应仲醇的ee分别为20–30和5％–6％，以及配置。提出了这种反演的合理机制。