(7aR,14S)-14-phenyl-7a,8,9,10,11,12-hexahydro-14H-naphtho-[1',2':5,6][1,3]oxazino[2,1-b]azepine | 500352-90-9

• 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,14S)-14-phenyl-7a,8,9,10,11,12-hexahydro-14H-naphtho-[1',2':5,6][1,3]oxazino[2,1-b]azepine
• 英文别名: (3R,10S)-10-phenyl-2-oxa-9-azatetracyclo[9.8.0.03,9.012,17]nonadeca-1(11),12,14,16,18-pentaene
• CAS: 500352-90-9
• 化学式: C₂₃H₂₃NO
• 分子量: 329.442
• InChiKey: SXXNXLGJWJMPPX-GGAORHGYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.8
• 重原子数：
  25
• 可旋转键数：
  1
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  12.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (7aR,14S)-14-phenyl-7a,8,9,10,11,12-hexahydro-14H-naphtho-[1',2':5,6][1,3]oxazino[2,1-b]azepine 在 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 为溶剂， 反应 1.5h， 以95%的产率得到(S)-1-(α-azepanylbenzyl)-2-naphthol
  参考文献：
  名称：

  Novel preparation of non-racemic 1-[α-(1-azacycloalkyl)benzyl]-2-naphthols from Betti base and their application as chiral ligands in the asymmetric addition of diethylzinc to aryl aldehydes

  摘要：

  开发了一种制备非外消旋的1-[α-(1-氮杂环烷基)苯基]-2-萘醇的创新路线，该方法涉及在NaBH3CN的存在下对Betti碱进行区域选择性的N-环烷基化，与二醛反应生成1-氮杂环烷基[2,1-b]噁唑，随后用LiAlH4选择性断裂C–O键。作为一种新的手性配体家族，我们测试了其在二乙基锌对芳基醛进行对映选择性加成中的应用。结合呱啉和哌啶的配体实现了高效的非对称诱导，生成的产物收率高达96%，对映体过量（ee）达到99%。

  DOI：

  10.1039/b204534f
• 作为产物：
  描述：

  (7aR,12R,14S)-12-(1-benzotriazolyl)-14-phenyl-7a,8,9,10,11,12-hexahydro-14H-naphtho[1',2':5,6][1,3]oxazino[2,1-b]azepine 在 sodium cyanoborohydride 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 生成 (7aR,14S)-14-phenyl-7a,8,9,10,11,12-hexahydro-14H-naphtho-[1',2':5,6][1,3]oxazino[2,1-b]azepine
  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

• Redox-Neutral α-Oxygenation of Amines: Reaction Development and Elucidation of the Mechanism
  作者：Matthew T. Richers、Martin Breugst、Alena Yu. Platonova、Anja Ullrich、Arne Dieckmann、K. N. Houk、Daniel Seidel

  DOI：10.1021/ja501988b

  日期：2014.4.23

  secondary amines and 2-hydroxybenzaldehydes or related ketones react to furnish benzo[e][1,3]oxazine structures in generally good yields. This overall redox-neutral amine α-C–H functionalization features a combined reductive N-alkylation/oxidative α-functionalization and is catalyzed by acetic acid. In contrast to previous reports, no external oxidants or metal catalysts are required. Reactions performed

  环状仲胺和 2-羟基苯甲醛或相关酮反应以通常良好的产率提供苯并[e][1,3]恶嗪结构。这种整体氧化还原中性胺 α-C-H 官能化具有还原 N-烷基化/氧化 α-官能化的组合，并由乙酸催化。与之前的报告相比，不需要外部氧化剂或金属催化剂。在改进的条件下进行的反应导致明显的还原胺化并在涉及氧化第二当量胺的过程中形成邻羟基苄胺。采用密度泛函理论的详细计算研究比较了不同的机械途径，并用于解释观察到的实验结果。此外，
• Divergent reaction: metal & oxidant free direct C–H aryloxylation and hydride free formal reductive N-benzylation of N-heterocycles
  作者：Sujit Mahato、Md Ashraful Haque、Soumita Dwari、Chandan K. Jana

  DOI：10.1039/c4ra05045b

  日期：——

  Metal, oxidant and other additive-free novel methods for direct C–H aryloxylation of aliphatic amines are developed. In the presence of excess amine, the course of the reaction was diverted, producing various arylmethylamines via hydride-free formal reductive amination. Involvement of a quinone methide intermediate was revealed from mechanistic studies.

  开发了金属，氧化剂和其他无添加剂的直接方法，用于脂肪胺的直接C–H芳氧基化。在过量胺的存在下，改变反应过程，通过无氢化物的正式还原胺化反应生成各种芳基甲胺。机理研究揭示了甲基苯醌中间体的参与。
• Synthesis of chiral ligands derived from the Betti base and their use in the enantioselective addition of diethylzinc to aromatic aldehydes
  作者：Jun Lu、Xuenong Xu、Cunde Wang、Jiangang He、Yuefei Hu、Hongwen Hu

  DOI：10.1016/s0040-4039(02)01985-8

  日期：2002.11

  A novel procedure for selective direct N,N-alkylation of the chiral Betti base was developed, and a new family of chiral ligands, (S)-1-(α-cycloaminobenzyl)-2-naphthols, were prepared. The ligands with five- and six-membered cyclic amines showed highly efficient asymmetric induction in the addition of diethylzinc to aromatic aldehydes in 93–96% yields and 91–99% ee.

  提出了一种新的选择性手性Betti碱直接N，N-烷基化的方法，并制备了一个新的手性配体家族，即（S）-1-（α-环氨基苄基）-2-萘酚。具有五元和六元环胺的配体在芳族醛中添加二乙基锌以93–96％的收率和91–99％ee的情况下显示出高效的不对称诱导。
• Iterative direct C_(sp3)–H functionalization of amines: diastereoselective divergent syntheses of α,α′-disubstituted alicyclic amines
  作者：Sujit Mahato、Chandan K. Jana

  DOI：10.1039/c6ob02257j

  日期：——

  A novel iterative C(sp3)–H oxygenation/C–C bond formation strategy, which avoids repetitive N-protection/-deprotection steps, was developed for direct α,α′-difunctionalization of alicyclic amines. The method is highly efficient and stereoselective in producing syn-α,α′-disubstituted aliphatic N-heterocycles. Synthetic potential and practicability of the method was demonstrated by an easy and straightforward

  针对脂环族胺的直接α，α′-双官能化，开发了一种新颖的迭代C （sp 3） -H氧合/ CC键形成策略，该方法避免了重复的N-保护/去保护步骤。该方法在产生顺-α，α′-二取代的脂族N-杂环上是高效且立体选择性的。合成电位和方法的实用性是由一个容易和简单的合成神经活性生物碱证明也不-lobelane及其衍生物。
• 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。