6-Formyl-3,4-dihydro-2H-pyridine-1-carboxylic acid tert-butyl ester | 146337-26-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: 6-Formyl-3,4-dihydro-2H-pyridine-1-carboxylic acid tert-butyl ester
• 英文别名: Tert-butyl 6-formyl-1,2,3,4-tetrahydropyridine-1-carboxylate；tert-butyl 6-formyl-3,4-dihydro-2H-pyridine-1-carboxylate
• CAS: 146337-26-0
• 化学式: C₁₁H₁₇NO₃
• 分子量: 211.261
• InChiKey: XCZFTMBURFLJOW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  46.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  lithium diphenyl cuprate 、 6-Formyl-3,4-dihydro-2H-pyridine-1-carboxylic acid tert-butyl ester 在 六甲基磷酰三胺 作用下， 以 四氢呋喃 为溶剂， 生成
  参考文献：
  名称：

  Trapping of carbolithiation-derived tertiary benzylic α-lithio piperidines with carbon electrophiles: Controlling the formation of α-amino quaternary and vicinal stereocenters

  摘要：

  通过对碳锂化衍生的三级苄基α锂吡啶与碳亲电试剂的拦截，实现了含α-氨基季碳立体中心的邻位官能化吡啶的对映选择性合成。

  DOI：

  10.1039/c5ob01371b
• 作为产物：
  描述：

  3-甲氧基哌啶-1-羧酸叔丁酯 、 alkaline earth salt of/the/ methylsulfuric acid 在 四甲基乙二胺 、 仲丁基锂 作用下， 生成 6-Formyl-3,4-dihydro-2H-pyridine-1-carboxylic acid tert-butyl ester
  参考文献：
  名称：

  .alpha.-Lithioamine synthetic equivalents: syntheses of diastereoisomers from Boc derivatives of cyclic amines

  摘要：

  Sequences of alpha'-lithiations and electrophilic substitutions of Boc-pyrrolidines, Boc-piperidines, and Boc-hexahydroazepines that provide compounds which are substituted adjacent to nitrogen are reported, and the pathways of the reactions are discussed. By this methodology monosubstituted 2 and disubstituted 2,4,2,6, and 2,5 Boc-piperidines are obtained as single or separable diastereoisomers consistent with equatorial lithiations and retentive electrophilic substitution in chair conformations. Both cis and trans 2,6-disubstituted diastereoisomers can be prepared, and control of diastereoselectivity is demonstrated by syntheses of solenopsin A, a 2,6-trans-disubstituted piperidine, and of Boc-dihydropinidine, a 2,6-cis-disubstituted piperidine. In the case of 3-methoxy-Boc-piperidine elimination of methoxide occurs upon lithiation, and with cis-2,4-disubstituted Boc-piperidines the electrophile is introduced with trans stereochemistry at C-6. These reactions are suggested to involve twist boat conformations consistent with an X-ray crystal structure of 2-methyl-6-(trimethylstannyl)-4-phenyl-N-Boc-piperidine. Boc-pyrrolidine lithiates more rapidly than Boc-piperidine, provides 2-substituted products with electrophiles, and on further lithiation-substitution gives 2,5-cis- and -trans-substituted products. Boc-perhydroazepine provides 2-substituted products by the sequence and on further lithiation-substitution gives 2,7-trans-disubstituted products.

  DOI：

  10.1021/jo00057a024

文献信息

• .alpha.-Lithioamine synthetic equivalents: syntheses of diastereoisomers from Boc derivatives of cyclic amines
  作者：Peter Beak、Won Koo Lee

  DOI：10.1021/jo00057a024

  日期：1993.2

  Sequences of alpha'-lithiations and electrophilic substitutions of Boc-pyrrolidines, Boc-piperidines, and Boc-hexahydroazepines that provide compounds which are substituted adjacent to nitrogen are reported, and the pathways of the reactions are discussed. By this methodology monosubstituted 2 and disubstituted 2,4,2,6, and 2,5 Boc-piperidines are obtained as single or separable diastereoisomers consistent with equatorial lithiations and retentive electrophilic substitution in chair conformations. Both cis and trans 2,6-disubstituted diastereoisomers can be prepared, and control of diastereoselectivity is demonstrated by syntheses of solenopsin A, a 2,6-trans-disubstituted piperidine, and of Boc-dihydropinidine, a 2,6-cis-disubstituted piperidine. In the case of 3-methoxy-Boc-piperidine elimination of methoxide occurs upon lithiation, and with cis-2,4-disubstituted Boc-piperidines the electrophile is introduced with trans stereochemistry at C-6. These reactions are suggested to involve twist boat conformations consistent with an X-ray crystal structure of 2-methyl-6-(trimethylstannyl)-4-phenyl-N-Boc-piperidine. Boc-pyrrolidine lithiates more rapidly than Boc-piperidine, provides 2-substituted products with electrophiles, and on further lithiation-substitution gives 2,5-cis- and -trans-substituted products. Boc-perhydroazepine provides 2-substituted products by the sequence and on further lithiation-substitution gives 2,7-trans-disubstituted products.
• Trapping of carbolithiation-derived tertiary benzylic α-lithio piperidines with carbon electrophiles: Controlling the formation of α-amino quaternary and vicinal stereocenters
  作者：Timothy K. Beng、Nathan Fox、Daniel P. Bassler、Amir Alwali、Kayla Sincavage、Ann Wens V. Silaire

  DOI：10.1039/c5ob01371b

  日期：——

  The interception of carbolithiation-derived tertiary benzylic α-lithio piperidines with carbon electrophiles has led to the diastereoselective synthesis of vicinally functionalized piperidines bearing α-amino quaternary stereocenters.

  通过对碳锂化衍生的三级苄基α锂吡啶与碳亲电试剂的拦截，实现了含α-氨基季碳立体中心的邻位官能化吡啶的对映选择性合成。