1-Boc-2-氮杂烷甲醛 | 146337-41-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氮杂环庚烷
• 中文名称: 1-Boc-2-氮杂烷甲醛
• 中文别名: 2-甲酰基氮杂环庚烷-1-甲酸叔丁酯
• 英文名称: tert-butyl 2-formyl-1-azepanecarboxylate
• 英文别名: Tert-butyl 2-formylazepane-1-carboxylate
• CAS: 146337-41-9
• 化学式: C₁₂H₂₁NO₃
• mdl: MFCD07776597
• 分子量: 227.304
• InChiKey: YYVXGCZFWGOISI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.833
• 拓扑面积：
  46.6
• 氢给体数：
  0
• 氢受体数：
  3

安全信息

• 海关编码：
  2933990090

反应信息

• 作为反应物：
  描述：

  1-Boc-2-氮杂烷甲醛 生成 2-(2-Ethoxycarbonyl-ethyl)-azepane-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
• 作为产物：
  描述：

  二碳酸二叔丁酯 在 四甲基乙二胺 、 仲丁基锂 作用下， 以 四氢呋喃 为溶剂， 反应 0.5h， 生成 1-Boc-2-氮杂烷甲醛
  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

• Formation of Unusual Seven-Membered Heterocycles Incorporating Nitrogen and Sulfur by Intramolecular Conjugate Displacement
  作者：Zhenhua Chen、Derrick L. J. Clive

  DOI：10.1021/jo101539m

  日期：2010.10.15

  be converted into unusual seven-membered heterocycles containing both nitrogen and sulfur by O-acylation (AcCl or EtOCOCl), N-deprotection (CF3CO2H), and reaction with CS2. In a modification of this process, when the original nitrogen is substituted in the form PhSCH2CON(Me), an azepine derivative is then generated. The ring closures occur by intramolecular conjugate displacement.

  衍生自丙烯酸甲酯或丙烯腈且在羟基上带有N-Boc基团β的Baylis-Hillman醇（CH（OH）CHNBoc）可以通过O-酰化反应转化为既含氮又含硫的不寻常的七元杂环（AcCl或EtOCOCl ），N-脱保护基（CF 3 CO 2 H）以及与CS 2的反应。在该方法的改进方案中，当原始氮以PhSCH 2 CON（Me）的形式被取代时，就会生成a庚因衍生物。闭环通过分子内共轭物置换发生。
• Studies on the aza-Claisen Rearrangement of 7 to 9-Membered Vinylazacycles
  作者：Jong-Wha Jung、Young-Ger Suh、Seok-Ho Kim、Won-Il Lee、Seon-Mi Kim、Jae-Kyung Jung、Jaebong Jang、Jaehoon Sim

  DOI：10.3987/com-16-13432

  日期：——

  A systematic study on the amide enolate-induced aza-Claisen rearrangement (ACR) of 7 to 9-membered vinylazacycles has been carried out, resulting in an efficient synthetic method to prepare 11 to 13-membered macrolactams. Key feature includes introduction of electron-donating substituents at a-position of the amide substrates possessing 7 to 9-membered vinylazacycles to facilitate amide enolate-induced.ACR. In addition, substituent effects on ACR has been discussed based on the experimental results. We believe this study would provide experimental evidences for the substituent effects and envision for the synthetic application of ACR-induced ring expansion.
• [EN] AZAHETEROCYCLES, COMBINATORY LIBRARY, FOCUSED LIBRARY, PHARMACEUTICAL COMPOSITION AND METHODS FOR THE PRODUCTION THEREOF<br/>[FR] BIBLIOTHÈQUES COMBINATOIRE ET FOCALISÉE D'AZAHÉTÉROCYCLES, COMPOSITION PHARMACEUTIQUE ET PROCÉDÉS DE LEUR FABRICATION
  申请人：CHEMICAL DIVERSITY RES INST LT

  公开号：WO2007117180A1

  公开（公告）日：2007-10-18

  [EN] The invention relates to novel azaheterocycles of interest as potential physiologically active substances (agonists, antagonists, receptor modulators, ferment inhibitors, oncolytics, antibacterial and antiparasitic agent etc.), to combinatory and focused libraries comprising novel azaheterocycles of a pharmaceutical composition containing said novel azaheterocycles in the form of an active substance and to methods for the production and the use thereof. Said novel azaheterocycles are of general formula (1), wherein W is an azaheterocycle which comprises 6-12 atoms, is optionally annelated, has at least one C₅-C₇ carbocycle and/or heterocycle, and also comprises at least one of heteroatoms and is selected from an O, S or N group; R₁
  [FR] L'invention concerne de nouveaux azahétérocycles qui représentent un intérêt certain en tant que substances physiologiquement actives potentielles (agonistes, antagonistes et modulateurs de récepteurs, inhibiteurs de ferments, oncolytiques, antibactériens, antiparasitaires, etc.), des bibliothèques combinatoire et focalisée comprenant de nouveaux azahétérocycles, une composition pharmaceutique contenant en tant que substance active de nouveaux azahétérocycles, leurs procédés de fabrication et d'utilisation. L'invention porte sur de nouveaux azahétérocycles ayant la formule générale (1), dans laquelle W est un hétérocycle comprenant de 6 à 12 atomes éventuellement hybridé à un carbocycle et/ou hétérocycle C₅-C₇, qui comprend au moins un hétéro-atome sélectionné dans le groupe O, S ou N, R₁
• .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.