(7aR,13S)-13-phenyl-8,9,10,11-tetrahydro-7aH,13H-naphtho[1,2-e]pyrido[2,1-b][1,3]oxazine | 500352-89-6

• 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,13S)-13-phenyl-8,9,10,11-tetrahydro-7aH,13H-naphtho[1,2-e]pyrido[2,1-b][1,3]oxazine
• 英文别名: (12R,18S)-18-phenyl-11-oxa-17-azatetracyclo[8.8.0.02,7.012,17]octadeca-1(10),2,4,6,8-pentaene
• CAS: 500352-89-6
• 化学式: C₂₂H₂₁NO
• 分子量: 315.415
• InChiKey: NKTURDWYUWMOKB-IRLDBZIGSA-N

物化性质

• 沸点：
  455.7±34.0 °C(Predicted)
• 密度：
  1.22±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.5
• 重原子数：
  24
• 可旋转键数：
  1
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.27
• 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,13S)-13-phenyl-8,9,10,11-tetrahydro-7aH,13H-naphtho[1,2-e]pyrido[2,1-b][1,3]oxazine 在 氢气 作用下， 以 乙醚 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：

  (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 sodium cyanoborohydride 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 生成 (7aR,13S)-13-phenyl-8,9,10,11-tetrahydro-7aH,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

• 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。
• Metal-free new synthesis of 1,3-naphthoxazines via intramolecular cross dehydrogenative-coupling reaction of 1-(α-aminoalkyl)-2-naphthols using hypervalent iodine(III) reagent
  作者：Nitin A. Waghmode、Amit H. Kalbandhe、Prerana B. Thorat、Nandkishor N. Karade

  DOI：10.1016/j.tetlet.2015.12.117

  日期：2016.2

  A series of 1-(α-aminoalkyl)-2-naphthols were synthesized via three-component Betti reaction of β-naphthol, aldehyde, and cyclic secondary amine under reflux conditions. The subsequent reactions of 1-(α-aminoalkyl)-2-naphthols with (diacetoxyiodo)benzene resulted in the formation of 1,3-napthoxazines. This reaction demonstrates the formation of CO bond via cross dehydrogenative-coupling (CDC) under

  通过β-萘酚，醛和环状仲胺在回流条件下的三组分Betti反应，合成了一系列1-（α-氨基烷基）-2-萘酚。1-（α-氨基烷基）-2-萘酚与（二乙酰氧基碘）苯的后续反应导致形成1,3-萘并恶嗪。该反应表明在无过渡金属的条件下通过交叉脱氢偶联（CDC）形成了C O键。
• 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。
• 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
  作者：Jun Lu、Xuenong Xu、Shaozhong Wang、Cunde Wang、Yuefei Hu、Hongwen Hu

  DOI：10.1039/b204534f

  日期：——

  A novel route for the preparation of non-racemic 1-[α-(1-azacycloalkyl)benzyl]-2-naphthols was developed, which involves regioselective N-cycloalkylation of the Betti base with dials in the presence of NaBH3CN to give 1-azacycloalka[2,1-b]oxazine followed by the selective cleavage of a C–O bond with LiAlH4. As a new family of chiral ligands, their application in the enantioselective addition of diethylzinc to aryl aldehydes was tested. The ligands incorporating pyrrolidine and piperidine led to highly efficient asymmetric induction to give products in up to 96% yield and 99% ee.

  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%。