(7aR,11R,13S)-11-(1H-benzotriazol-1-yl)-7a,8,10,11-tetrahydro-13-phenyl-9H,13H-naphtho[1,2-e]pyrido[2,1-b][1,3]oxazine | 667870-42-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并恶嗪类
• 英文名称: (7aR,11R,13S)-11-(1H-benzotriazol-1-yl)-7a,8,10,11-tetrahydro-13-phenyl-9H,13H-naphtho[1,2-e]pyrido[2,1-b][1,3]oxazine
• 英文别名: (7aR,11R,13S)-11-(1-benzotriazolyl)-13-phenyl-8,9,10,11-tetrahydro-7aH,13H-naphtho[1.2-e]pyrido[2,1-b][1,3]oxazine；(12R,16R,18S)-16-(benzotriazol-1-yl)-18-phenyl-11-oxa-17-azatetracyclo[8.8.0.02,7.012,17]octadeca-1(10),2,4,6,8-pentaene
• CAS: 667870-42-0
• 化学式: C₂₈H₂₄N₄O
• 分子量: 432.525
• InChiKey: HMHMVBTWABNOEW-GTNKKZTPSA-N

物化性质

• 沸点：
  630.5±55.0 °C(Predicted)
• 密度：
  1.34±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.4
• 重原子数：
  33
• 可旋转键数：
  2
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.21
• 拓扑面积：
  43.2
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (7aR,11R,13S)-11-(1H-benzotriazol-1-yl)-7a,8,10,11-tetrahydro-13-phenyl-9H,13H-naphtho[1,2-e]pyrido[2,1-b][1,3]oxazine 在 氢气 、 sodium cyanoborohydride 作用下， 以 甲醇 、 乙醚 、 二氯甲烷 为溶剂， 反应 0.5h， 生成 (R)-2-丙基哌啶
  参考文献：
  名称：

  Diastereopure Preparation of α-Benzotriazolyl 1-Azacycloalka[2,1-b][1,3]-oxazines and their Application as Versatile Chiral Precursors

  摘要：

  制备了一组非外消旋的贝蒂碱衍生的立体纯α-苯并三氮唑基1-氮杂环烷[2,1-b][1,3]恶嗪。这些化合物被用作制备手性配体和手性取代氮杂环化合物的前体，具有显著的立体选择性优势。

  DOI：

  10.1055/s-2003-43353
• 作为产物：
  描述：

  T406石油添加剂 、 戊二醛 、 (S)-1-(α-aminobenzyl)-2-naphthol L-(+)-tartrate 以 二氯甲烷 为溶剂， 反应 5.0h， 以91%的产率得到(7aR,11R,13S)-11-(1H-benzotriazol-1-yl)-7a,8,10,11-tetrahydro-13-phenyl-9H,13H-naphtho[1,2-e]pyrido[2,1-b][1,3]oxazine
  参考文献：
  名称：

  Diastereopure Preparation of α-Benzotriazolyl 1-Azacycloalka[2,1-b][1,3]-oxazines and their Application as Versatile Chiral Precursors

  摘要：

  制备了一组非外消旋的贝蒂碱衍生的立体纯α-苯并三氮唑基1-氮杂环烷[2,1-b][1,3]恶嗪。这些化合物被用作制备手性配体和手性取代氮杂环化合物的前体，具有显著的立体选择性优势。

  DOI：

  10.1055/s-2003-43353

文献信息

• Enantiopure 2,6-disubstituted piperidines bearing one alkene- or alkyne-containing substituent: preparation and application to total syntheses of indolizidine-alkaloids
  作者：Hui Liu、Deyong Su、Guolin Cheng、Jimin Xu、Xinyan Wang、Yuefei Hu

  DOI：10.1039/b927007h

  日期：——

  general and efficient procedure for the preparation of 2,6-disubstituted piperidines bearing one alkene- or alkyne-containing substituent was developed by using non-racemic Betti base as a chiral auxiliary. Many chiral benzylamines are excellent auxiliaries, but they were rarely used for this purpose because of the inefficient removal of the N-benzyl auxiliary residue under non-hydrogenative conditions

  通过使用非外消旋的Betti碱作为手性助剂，开发了一种制备带有一个含烯烃或炔烃取代基的2,6-二取代哌啶的通用有效方法。许多手性苄胺是极好的助剂，但由于在非氢化条件下不能有效去除N-苄基辅助残基，因此很少用于此目的。我们发现ñ，ñ-二取代的贝蒂碱衍生物具有典型的曼尼希结构 邻萘酚。当它进行碱催化的生成时邻醌甲基化物，实现了有效的非氢化N-脱苄基作用，并且烯烃和炔烃基团得以幸存。为了证明该方法的有效性和产品的多功能性，采用了不对称的总合成方法吲哚嗪-生物碱 （-）-167B， （-）-195小时， （-）-209D 和 （-）-223AB 完成了。
• Total Synthesis of (+)-Epilupinine via An Intramolecular Nitrile Oxide-Alkene Cycloaddition
  作者：Deyong Su、Xinyan Wang、Changwei Shao、Jimin Xu、Rui Zhu、Yuefei Hu

  DOI：10.1021/jo101910r

  日期：2011.1.7

  (R)-(2-vinylpiperid-1-yl)propanal by routine methods. Thus, by using Fukuyama’s oxime synthesis, a general method was developed for highly efficient conversion of 3-(N,N-dialkylamino)propanols into 3-(N,N-dialkylamino)propanal oximes without using the corresponding aldehydes.

  （+）-癫痫素的全合成以9个步骤完成，总产率为48％，其中将INOC用作构建喹喔啉骨架的关键步骤。我们发现通过常规方法制备关键中间体（R）-N-（3-硝基丙基）-2-乙烯基哌啶或（R）-（2-乙烯基哌啶-1-基）丙醛是极其困难的任务。因此，通过使用福山的肟合成法，开发了一种不使用相应的醛就能将3-（N，N-二烷基氨基）丙醇高效转化为3-（N，N-二烷基氨基）丙肟的通用方法。
• Nonracemic Betti Base as a New Chiral Auxiliary:  Application to Total Syntheses of Enantiopure (2<i>S</i>,6<i>R</i>)-Dihydropinidine and (2<i>S</i>,6<i>R</i>)-Isosolenopsins
  作者：Xinyan Wang、Yanmei Dong、Jianwei Sun、Xuenong Xu、Rui Li、Yuefei Hu

  DOI：10.1021/jo0480444

  日期：2005.3.1

  Total syntheses of enantiopure alkaloidal natural products (2S,6R)-dihydropinidine (as hydrochloride) and (2S,6R)isosolenopsins (as hydrochlorides) were achieved in four steps and in 80-82% total yields by using a synthetic strategy of the formation-cleavage of 1,3-oxazinane. (S)-Betti base was proved to be an excellent chiral auxiliary and a novel Pd/C catalyzed N-debenzylation straightforward to amine hydrochloride was developed in the presence of CH2Cl2.
• An improved synthesis of chiral 1-[α-(1-azacycloalkyl)benzyl]-2-naphthols
  作者：Xuenong Xu、Jun Lu、Yanmei Dong、Rui Li、Zongming Ge、Yuefei Hu

  DOI：10.1016/j.tetasy.2003.12.025

  日期：2004.2

  An improved synthesis of homochiral 1-[alpha-(1-azacycloalkyl)benzyl]-2-naphthols and 1-[alpha-(2-arylpiperidyl)benzyl]-2-naphthols has been achieved by employing diastereomerically pure alpha-benzotriazolyl 1-azacycloalka[2,1-b][1,3]oxazines as homochiral precursors, which were obtained by condensation between nonracemic Betti base and dialdehydes in the presence of benzotriazole. (C) 2003 Elsevier Ltd. All rights reserved.
• Diastereopure Preparation of α-Benzotriazolyl 1-Azacycloalka[2,1-<i>b</i>][1,3]-oxazines and their Application as Versatile Chiral Precursors
  作者：Yuefei Hu、Xuenong Xu、Jun Lu、Rui Li、Zongming Ge、Yanmei Dong

  DOI：10.1055/s-2003-43353

  日期：——

  A group of diastereopure α-benzotriazolyl 1-azacyclo­alka[2,1-b][1,3]oxazines were prepared from non-racemic Betti base and they were employed as the versatile precursors for the preparation of chiral ligands and chiral substituted azacyclics with significant advantages in the stereoselectivity.

  制备了一组非外消旋的贝蒂碱衍生的立体纯α-苯并三氮唑基1-氮杂环烷[2,1-b][1,3]恶嗪。这些化合物被用作制备手性配体和手性取代氮杂环化合物的前体，具有显著的立体选择性优势。