(5S)-methyl 5-(tert-butyldimethylsilanyloxy)-2-oxopiperidine-1-carboxylate | 138565-91-0

• 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: (5S)-methyl 5-(tert-butyldimethylsilanyloxy)-2-oxopiperidine-1-carboxylate
• 英文别名: methyl (S)-5-(tert-butyldimethylsilyloxy)-2-oxopiperidine-1-carboxylate；(5S)-5-t-butyldimethylsilyloxy-N-methoxycarbonyl-2-piperidinone；Methyl (S)-5-((tert-butyldimethylsilyl)oxy)-2-oxopiperidine-1-carboxylate；methyl (5S)-5-[tert-butyl(dimethyl)silyl]oxy-2-oxopiperidine-1-carboxylate
• CAS: 138565-91-0
• 化学式: C₁₃H₂₅NO₄Si
• 分子量: 287.431
• InChiKey: XMDUPNQNYAHSLO-JTQLQIEISA-N

物化性质

• 沸点：
  356.6±35.0 °C(Predicted)
• 密度：
  1.04±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.77
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  55.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (5S)-methyl 5-(tert-butyldimethylsilanyloxy)-2-oxopiperidine-1-carboxylate 在 臭氧 、 zinc dibromide 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 4.33h， 生成 (5S)-3-(benzyloxycarbonyl)-5-(tert-butyldimethylsilyloxy)-1-(methoxycarbonyl)-4-[4-oxo-2(E)-buten-1-yl]-2-piperidone
  参考文献：
  名称：

  Diels–Alder Reactions of 5,6-Dihydro-2(1H)-pyridones

  摘要：

  The Diels-Alder reaction of achiral 5,6-dihydro-2(1H)-pyridones 12a,b and enantiopure 5,6-dihydro-2(1H)-pyridones 16a,b with a variety of diversely substituted buta-1,3-dienes under thermal or catalytic conditions, to give partially reduced isoquinolones 18-33 and 35-37, is reported. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(00)00317-3
• 作为产物：
  描述：

  (S)-5-羟基哌啶-2酮 在 咪唑 、 正丁基锂 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 生成 (5S)-methyl 5-(tert-butyldimethylsilanyloxy)-2-oxopiperidine-1-carboxylate
  参考文献：
  名称：

  Synthesis of unnatural 2R,5S-5-hydroxypipecolic acid via homochiral acyliminium ion - pipecolic acids - part III.

  摘要：

  Stereoselective functionalization of S-5-hydroxy-2-piperidone 1 via acyliminium ion was demonstrated to maintain the unnatural enantiomer of trans-5-hydroxypipecolic acid 6.

  DOI：

  10.1016/s0957-4166(00)86132-7

文献信息

• Complementary and Stereodivergent Approaches to the Synthesis of 5-Hydroxy- and 4,5-Dihydroxypipecolic Acids from Enantiopure Hydroxylated Lactams
  作者：Dina Scarpi、Laura Bartali、Andrea Casini、Ernesto G. Occhiato

  DOI：10.1002/ejoc.201201429

  日期：2013.3

  describe two complementary and stereodivergent routes, from commercially available and inexpensive starting materials, for the synthesis of 4,5-dihydroxy- and 5-hydroxypipecolic acids based on the chemistry of lactam-derived enol phosphates. The synthesis of the 4,5-cis-4,5-dihydroxypipecolic acids required the preparation from 2-deoxy-D- and -L-ribose of the enantiopure cis-(4S,5R)- and -(4R,5S)-4

  我们描述了两种互补和立体发散的路线，从市售和廉价的起始材料中，基于内酰胺衍生的烯醇磷酸酯的化学合成 4,5-二羟基和 5-羟基哌啶酸。4,5-顺式-4,5-二羟基哌啶酸的合成需要从对映体纯顺式-(4S,5R)-和-(4R,5S)-的2-脱氧-D-和-L-核糖制备分别为 4,5-二羟基-δ-戊内酰胺。这些新的手性合成子可用于合成其他天然产物。关键步骤是由这些内酰胺生成的烯醇磷酸酯的 Pd 催化甲氧基羰基化反应。该反应提供的烯氨基甲酸酯很容易通过立体选择性还原转化为目标化合物。4,5-反式-4,5-二羟基哌可酸的合成，以及 5-羟基哌啶酸，由已知的 (S)-5-羟基-δ-戊内酰胺衍生物实现，对于二羟基化合物，需要对烯醇甲氧基羰基化获得的烯氨基甲酸酯进行高度立体选择性烯丙基溴化反应磷酸盐。从 2-脱氧-L-核糖制备顺式-4,5-二羟基-δ-戊内酰胺的 (4R,5S) 对映体，同时可以制备 (R)-5-羟基-δ-戊内酰胺来自
• Synthesis of 2S,5S-and 2R,5S-5-hydroxypipecolic acid via amide-methylenation of S-5-hydroxy-2-piperidone with dimethyltitanocene.
  作者：Claus Herdeis、Eberhard Heller

  DOI：10.1016/s0957-4166(00)82257-0

  日期：1993.1

  A route to 2S,5S-and 2R,5S-hydroxypipecolic acid is presented, starting with the enantiopure 5S-5-hydroxy-piperidone 7. The key step of this reaction sequence is the chemoselective methylenation of the amide carbonyl group of 8 with dimethyltitanocene 9 to 10. The transformation of the exocyclic enecarbamate double bond to the carboxylic acid group is best accomplished via hydroboration/oxidation to the alcohol 11a,b. Separation and oxidation of the diastereomers 11a,b, to 14a, and 14b, and hydrolysis furnishes the diastereomeric pipecolic acids 15a and 15b in enantiopure form.
• Herdeis, Claus; Held, Walter A.; Kirfel, Armin, Liebigs Annalen der Chemie, 1994, # 11, p. 1117 - 1120
  作者：Herdeis, Claus、Held, Walter A.、Kirfel, Armin

  DOI：——

  日期：——
• Synthesis of unnatural 2R,5S-5-hydroxypipecolic acid via homochiral acyliminium ion - pipecolic acids - part III.
  作者：C. Herdeis、W. Engel

  DOI：10.1016/s0957-4166(00)86132-7

  日期：1991.1

  Stereoselective functionalization of S-5-hydroxy-2-piperidone 1 via acyliminium ion was demonstrated to maintain the unnatural enantiomer of trans-5-hydroxypipecolic acid 6.
• Diels–Alder Reactions of 5,6-Dihydro-2(1H)-pyridones
  作者：Núria Casamitjana、Virginia López、Angela Jorge、Joan Bosch、Elies Molins、Anna Roig

  DOI：10.1016/s0040-4020(00)00317-3

  日期：2000.6

  The Diels-Alder reaction of achiral 5,6-dihydro-2(1H)-pyridones 12a,b and enantiopure 5,6-dihydro-2(1H)-pyridones 16a,b with a variety of diversely substituted buta-1,3-dienes under thermal or catalytic conditions, to give partially reduced isoquinolones 18-33 and 35-37, is reported. (C) 2000 Elsevier Science Ltd. All rights reserved.