4-methyl-4,5-dihydro-3H-4-azacyclohepta[2,1-a:3,4-a']dinaphthalene | 97781-21-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯氮卓类
• 英文名称: 4-methyl-4,5-dihydro-3H-4-azacyclohepta[2,1-a:3,4-a']dinaphthalene
• 英文别名: 13-Methyl-13-azapentacyclo[13.8.0.02,11.03,8.018,23]tricosa-1(15),2(11),3,5,7,9,16,18,20,22-decaene
• CAS: 97781-21-0
• 化学式: C₂₃H₁₉N
• 分子量: 309.411
• InChiKey: TUYNPLTXSRUVLR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.5
• 重原子数：
  24
• 可旋转键数：
  0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.13
• 拓扑面积：
  3.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  4-methyl-4,5-dihydro-3H-4-azacyclohepta[2,1-a:3,4-a']dinaphthalene 在 磷酸三甲酯 、 lithium iodide 、 18-冠醚-6 、 potassium tert-butylate 作用下， 以 四氢呋喃 为溶剂， 以87 %的产率得到(5)螺烯
  参考文献：
  名称：

  用于合成多环杂芳烃的脱氨基环收缩：托达喹啉的简明全合成

  摘要：

  详细介绍了涉及脱氨基收缩级联的制备多环杂芳烃的简明策略。有效的脱氨环收缩涉及联芳基连接的二氢吖庚因的原位甲基化，形成环状铵阳离子，该阳离子经历碱诱导的[1,2]-史蒂文斯重排/脱氢氨化序列。假对称性的存在指导了含吡啶基多环杂芳烃的逆合成分析，使其能够通过叔胺前体的还原环化和脱氨收缩来构建。

  DOI：

  10.1039/d3sc03936f
• 作为产物：
  描述：

  (1R,2S)-2-(13-methyl-13-azoniapentacyclo[13.8.0.02,11.03,8.018,23]tricosa-1(15),2(11),3,5,7,9,16,18,20,22-decaen-13-yl)-1-phenylpropan-1-ol;bromide 以100%的产率得到
  参考文献：
  名称：

  Stara Irena G., Star Ivo, Zavada Jii, Tetrahedron, 3 (1992) N 11, S 1365-1368

  摘要：

  DOI：

文献信息

• Asymmetric Aziridination of Chalcone Promoted by Binaphthalene-Based Chiral Amines
  作者：Philip Page、Céline Bordogna、Ian Strutt、Yohan Chan、Benjamin Buckley

  DOI：10.1055/s-0033-1339643

  日期：——

  binaphthalene-based tertiary amines have been used for the asymmetric aziridination of chalcone, providing N-unprotected aziridines with ee values of up to 43%. A chiral hydrazinium salt has been isolated for the first time and shown to provide similar yield and enantioselectivity to the in situ process in reaction with chalcone.

  原位衍生自许多对映异构纯的联萘叔胺的胺已用于查耳酮的不对称氮丙啶化，提供 N-未保护的氮丙啶，其 ee 值高达 43%。首次分离出手性肼盐，并显示出与原位与查耳酮反应过程相似的产率和对映选择性。
• Reductive cleavage of axially disymmetric tertiary amines and quaternary ammonium salts by lithium aluminium hydride. Synthesis of new 1,1′-binaphthyl substituted amines
  作者：Frédéric Cottineau、Nicole Maigrot、Jean-Paul Mazaleyrat

  DOI：10.1016/s0040-4039(00)61900-7

  日期：1985.1

  Axially disymmetric tertiary amines or quaternary ammonium salts A are synthesized by double alkylation of primary or secondary amines with racemic or optically pure 2,2′-bis (bromomethyl)-1,1′-binaphthyl. Their reductive cleavage by lithium aluminium hydride in refluxing THF leads to chiral secondary or tertiary amines B, substituted by a binaphthyl unit, with high yields and absence of racemization

  轴向二对称的叔胺或季铵盐A是通过将伯胺或仲胺与外消旋或光学纯的2,2'-双（溴甲基）-1,1'-联萘基进行双烷基化反应而合成的。它们在回流的THF中被氢化铝锂还原裂解，得到手性仲或叔胺B，被双萘基单元取代，收率高且没有外消旋作用。
• Ring-Expansion Reactions of Binaphthyl Azepines and Ferrocenophanes through Metal-Catalyzed [1,2]-Stevens Rearrangements
  作者：Jérôme Lacour、Steven Harthong、Renaud Bach、Céline Besnard、Laure Guénée

  DOI：10.1055/s-0033-1339188

  日期：——

  copper-catalyzed reaction of binaphthyl azepines and α-diazo carbonyl reagents. The [1,2]-Stevens rearrangement is general (61–93% yields) and can be extended to [3]ferrocenophanes; similar reactivity in favor of the products of ring expansion is obtained with these ferrocene derivatives (80–96% yields). Enantiopure binaphthyl azocines can be prepared in a single step via the direct copper-catalyzed reaction of

  摘要 对映纯双萘甲酰偶氮胺可通过双萘甲双胍和α-重氮羰基试剂的直接铜催化反应一步制备。[1,2]-史蒂文斯重排是一般的（61-93％的产率），可以扩展到[3]二茂铁。这些二茂铁衍生物获得了类似的反应性，从而有利于环的扩环（产率80-96％）。 对映纯双萘甲酰偶氮胺可通过双萘甲双胍和α-重氮羰基试剂的直接铜催化反应一步制备。[1,2]-史蒂文斯重排是一般的（61-93％的产率），可以扩展到[3]二茂铁。这些二茂铁衍生物获得了类似的反应性，从而有利于环的扩环（产率80-96％）。
• Nucleophilic Attack on 4,5-Dihydro-4-alkyl-3H-dinaphtho[2,1-c:1',2'-e]thiepinium Salts. A Convenient Approach to New 2,2'-Bidentate 1,1'-Binaphthalene Ligands with Sulfur Donor Atoms
  作者：Irena G. Stara、Ivo Stary、Milos Tichy、Jiri Zavada、Pavel Fiedler

  DOI：10.1021/jo00085a021

  日期：1994.3

  The title dihydrothiepinium salts 6 react with a wide range of N-, S-, Se-, O-, and C-nucleophiles to afford dihydrothiepin 5 and/or the corresponding bidentate ligands 7. The dual course of the reaction can be controlled by a judicious choice of the substrate counterion. In most instances, an iodide counterion aids formation of dihydrothiepins 5, whereas perchlorate, tetraphenyl borate, or tetrafluoroborate counterions favor formation of bidentate ligands 7. An explanation based on a competition between the counterion and the external nucleophile is provided. Dihydrothiepinium salts 6 are easily accessible from dibromide (R,S)-4 via dihydrothiepin (R,S)-5. Individual enantiomers (R)- and (S)-5 have been obtained by resolution on a preparative triacetylcellulose (TAC) column and assigned absolute configuration on the basis of CD spectra and chemical correlation.
• COTTINEAU, F.;MAIGROT, N.;MAZALEYRAT, J. -P., TETRAHEDRON LETT., 1985, 26, N 4, 421-424
  作者：COTTINEAU, F.、MAIGROT, N.、MAZALEYRAT, J. -P.

  DOI：——

  日期：——