(2R,2'R,6'R)-(-)-1-(6'-methylpiperidin-2'-yl)-2-(tert-butyldiphenylsilyloxy)propane | 350237-04-6

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (2R,2'R,6'R)-(-)-1-(6'-methylpiperidin-2'-yl)-2-(tert-butyldiphenylsilyloxy)propane
• 英文别名: (2R,2'R,6'R)-1-(6'-methylpiperidin-2'-yl)-2-tert-butyldiphenylsilyloxypropane；tert-butyl-[(2R)-1-[(2R,6R)-6-methylpiperidin-2-yl]propan-2-yl]oxy-diphenylsilane
• CAS: 350237-04-6
• 化学式: C₂₅H₃₇NOSi
• 分子量: 395.66
• InChiKey: DDAAFUGLBXBOOE-YPAWHYETSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.87
• 重原子数：
  28
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.52
• 拓扑面积：
  21.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (2R,2'R,6'R)-(-)-1-(6'-methylpiperidin-2'-yl)-2-(tert-butyldiphenylsilyloxy)propane 在 氢氧化钾 作用下， 以 甲醇 为溶剂， 反应 9.0h， 生成 (-)-pinidinol
  参考文献：
  名称：

  A Diastereoselective Intramolecular Hydroamination Approach to the Syntheses of (+)-, (±)-, and (−)-Pinidinol

  摘要：

  A diastereoselective, lanthanocene-catalyzed, intramolecular hydroamination reaction was applied to the preparation of 2,6-disubstituted piperidines. Various metal/ligand arrays in the catalysts were examined using a model substrate to allow optimization of the diastereoselectivity. It was determined that the relationship between metal size and ligand bulk plays an integral role in the transformation. The complex Cp*2NdCH(TMS)(2) converted 2-substituted 8-nonen-4-amines to 2,6-disubsituted piperidines with greater than 100:1 selectivity for the formation of the cis isomer. A short synthesis of pinidinol, an alkaloid isolated from various pine and spruce species, was then carried out to exploit this stereoselective reaction.

  DOI：

  10.1021/jo015603n
• 作为产物：
  描述：

  5-碘-1-戊烯 在 咪唑 、 sodium tetrahydroborate 、 正丁基锂 、 无水碳酸镉 、 Cp*2NdCH(SiMe₃)2 、 水 、 三苯基膦 、 mercury dichloride 、 偶氮二甲酸二乙酯 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 、 氘代苯 、 水 、 N,N-二甲基甲酰胺 、 异丙醇 、 乙腈 为溶剂， 生成 (2R,2'R,6'R)-(-)-1-(6'-methylpiperidin-2'-yl)-2-(tert-butyldiphenylsilyloxy)propane
  参考文献：
  名称：

  A Diastereoselective Intramolecular Hydroamination Approach to the Syntheses of (+)-, (±)-, and (−)-Pinidinol

  摘要：

  A diastereoselective, lanthanocene-catalyzed, intramolecular hydroamination reaction was applied to the preparation of 2,6-disubstituted piperidines. Various metal/ligand arrays in the catalysts were examined using a model substrate to allow optimization of the diastereoselectivity. It was determined that the relationship between metal size and ligand bulk plays an integral role in the transformation. The complex Cp*2NdCH(TMS)(2) converted 2-substituted 8-nonen-4-amines to 2,6-disubsituted piperidines with greater than 100:1 selectivity for the formation of the cis isomer. A short synthesis of pinidinol, an alkaloid isolated from various pine and spruce species, was then carried out to exploit this stereoselective reaction.

  DOI：

  10.1021/jo015603n

文献信息

• Asymmetric Synthesis of Acyclic 1,3-Amino Alcohols by Reduction of <i>N</i>-Sulfinyl β-Amino Ketones. Formal Synthesis of (−)-Pinidinol and (+)- Epipinidinol
  作者：Franklin A. Davis、Paul M. Gaspari、Brad M. Nolt、Peng Xu

  DOI：10.1021/jo801653c

  日期：2008.12.19

  Stereoselective reduction of acyclic N-sulfinyl beta-amino ketones with (LiEt(3)BH) and Li(t-BuO)(3)AlH, respectively, gave anti- and syn-1,3-amino alcohols with excellent selectivity. A formal asymmetric synthesis of the hydroxy piperidine alkaloids (-)-pinidinol and (+)-epipinidinol from a common N-sulfinyl beta-amino ketone ketal precursor was developed. The pinidinol piperidine ring was formed

  分别用（LiEt（3）BH）和Li（t-BuO）（3）AlH立体选择性还原无环N-亚磺酰基β-氨基酮，得到具有优异选择性的抗和syn-1,3-氨基醇。从常见的N-亚磺酰基β-氨基酮缩酮前体开发了羟基哌啶生物碱（-）-吡啶醇和（+）-哌啶醇的形式不对称合成。吡啶醇哌啶环是通过N-亚磺酰基氨基甲硅烷基保护的醇缩酮的新型酸催化级联反应形成的。