N-苄基-N-(叔丁氧羰基)-2-(2-氧代-1,2-二氢喹啉-4-基)乙胺 | 831176-42-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 喹啉及其衍生物
• 中文名称: N-苄基-N-(叔丁氧羰基)-2-(2-氧代-1,2-二氢喹啉-4-基)乙胺
• 英文名称: N-benzyl-N-(tert-butoxycarbonyl)-2-(2-oxo-1,2-dihydroquinolin-4-yl)ethylamine
• 英文别名: tert-butyl N-benzyl-N-[2-(2-oxo-1,2-dihydro-4-quinolinyl)ethyl]carbamate；N-benzyl-N-tert-butyloxycarbonyl-4-(2'-aminoethyl)quinolone；tert-butyl N-benzyl-N-[2-(2-oxo-1H-quinolin-4-yl)ethyl]carbamate
• CAS: 831176-42-2
• 化学式: C₂₃H₂₆N₂O₃
• 分子量: 378.471
• InChiKey: TYKDITICEHVBIT-UHFFFAOYSA-N

物化性质

• 熔点：
  149-151 °C
• 沸点：
  566.7±50.0 °C(Predicted)
• 密度：
  1.153±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  28
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  58.6
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  N-苄基-N-(叔丁氧羰基)-2-(2-氧代-1,2-二氢喹啉-4-基)乙胺 在 三氟乙酸 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 5.0h， 生成 rac-(1aS,7bS,11aS)-10-benzyl-1,9,10,11a-tetrahydro-1aH-pyrido[4',3':2,3']-cyclobuta[1,2-c]quinoline-2,11(3H,8H)-dione
  参考文献：
  名称：

  4-(2'-氨基乙基)喹诺酮的立体选择性分子内和分子间[2+2]光环加成反应

  摘要：

  4-(2'-氨基乙基)喹诺酮6、8和9以4-(2'-溴乙基)喹诺酮(4)为原料，分两步制备，总产率为56-93%。他们与烯烃进行分子间和分子内 [2+2] 光环加成反应，以提供外消旋形式的环丁烷 1-3（产率 61-89%）。光化学反应以非常好的化学选择性、区域选择性和立体选择性进行。在一种情况下 (8b → 2b) 也进行了对映选择性 (93% ee)。

  DOI：

  10.1055/s-2004-834817
• 作为产物：
  描述：

  2-羟基-4-甲基喹啉 在 lithium aluminium tetrahydride 、 正丁基锂 、 氯化亚砜 、 氢溴酸 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 4.0h， 生成 N-苄基-N-(叔丁氧羰基)-2-(2-氧代-1,2-二氢喹啉-4-基)乙胺
  参考文献：
  名称：

  Photochemistry of 4-(2‘-Aminoethyl)quinolones:  Enantioselective Synthesis of Tetracyclic Tetrahydro-1aH-pyrido[4‘,3‘:2,3]- cyclobuta[1,2-c] Quinoline-2,11(3H,8H)-diones by Intra- and Intermolecular [2 + 2]-Photocycloaddition Reactions in Solution

  摘要：

  Enantioselective [2 + 2]-photocycloaddition reactions on 4-(2'-aminoethyl) quinolones in solution were studied using the enantiomerically pure complexing agent 1 as source of chirality. The intermolecular reactions of fully N-protected substrates 5a-5c with different 2-alkyl-substituted acrylates 12-15 represent the first systematic study on the diastereoselectivity of their intermolecular [2 + 2]-photocycloadditions to unsymmetrically 1,1-disubstituted olefins (75-91% yield, d.r. = 58/42-95/5). N-Benzylic-protected photoproducts exo-16a/b-19a/b could easily be converted into lactams 20a/b-23a/b by a sequence of Boc deprotection and thermal lactamization (74-98% yield). Identical products 20a-22a were directly accessible by the intramolecular [ 2 + 2]-photocycloaddition of acrylic acid amides 2-4 (41-61% yield). The suitability of both pathways for an enantioselective reaction variant was proven (70-92% ee). Thus, tetracyclic lactams possessing the carbon framework C were obtained with good yields and enantio-selectivities of up to 92% ee in intramolecular reactions. Comparative investigation of both routes showed that quinolone dimerization was the single most decisive factor preventing a complete chirality transfer. Functional group manipulations were successfully conducted with the primary photoproduct exo-17a. Finally, a new and unexpected type of benzylic hydrogen abstraction-radical cyclization reaction was discovered for substrate 5a, which explains the photochemical instability of substrates 2-5 under short wavelength irradiation (lambda = 300 nm).

  DOI：

  10.1021/jo0606608

文献信息

• Stereoselective Intra- and Intermolecular [2+2] Photocycloaddition Reactions of 4-(2′-Aminoethyl)quinolones
  作者：Thorsten Bach、Sebastian Brandes、Philipp Selig

  DOI：10.1055/s-2004-834817

  日期：——

  The 4-(2'-aminoethyl)quinolones 6, 8 and 9 were prepared starting from 4-(2'-bromoethyl)quinolone (4) in two steps and overall yields of 56-93%. They underwent inter- and intramolecular [2+2] photocycloaddition reactions with an alkene to provide the cyclobutanes 1-3 in racemic form (61-89% yield). The photochemical reaction proceeded with very good chemo-, regio- and stereoselectivity. It was in one

  4-(2'-氨基乙基)喹诺酮6、8和9以4-(2'-溴乙基)喹诺酮(4)为原料，分两步制备，总产率为56-93%。他们与烯烃进行分子间和分子内 [2+2] 光环加成反应，以提供外消旋形式的环丁烷 1-3（产率 61-89%）。光化学反应以非常好的化学选择性、区域选择性和立体选择性进行。在一种情况下 (8b → 2b) 也进行了对映选择性 (93% ee)。
• Total Synthesis of Meloscine by a [2+2]-Photocycloaddition/Ring-Expansion Route
  作者：Philipp Selig、Eberhardt Herdtweck、Thorsten Bach

  DOI：10.1002/chem.200802383

  日期：2009.3.23

  The stereogenic centers at C3 and C12 of meloscine (3) can be established in the photochemical key step 1 → 2. 1,2‐retro‐Benzilic acid rearrangement to a five‐membered ring, reductive amination, Claisen rearrangement, and ring‐closing metathesis are further key steps in the transformation of cyclobutane 2 into the target molecule 3 (14 steps, 9 % overall yield). Enantioselective access to (+)‐meloscine

  可以在光化学关键步骤1 → 2中建立甲磺胺（3）的C3和C12的立体定向中心。1,2-复古-Benzilic酸重排一个五元环，还原性胺化，Claisen重排，和闭环复分解是在环丁烷的转化进一步关键步骤2到目标分子3（14个步骤，9％总产率）。当[2 + 2]-光环加成反应是在手性模板存在下进行时，对映体可以选择性地与（+）-肌氨酸结合。
• Cyclobutane Ring Opening Reactions of 1,2,2a,8b-Tetrahydrocyclobuta[<i>c</i>]-quinolin-3(4<i>H</i>)-ones
  作者：Thorsten Bach、Philipp Selig

  DOI：10.1055/s-2008-1067143

  日期：2008.7

  bond in the title compounds. The first reaction was found by serendipity when reductive debenzylation was attempted on a heteroanellated azabicyclo[4.2.0]octane. It yielded an eight-membered lactam ring (azocane). The second transformation relies on a rationally designed 1,2-rearrangement reaction, which was introduced because attempts to induce classical Wagner-Meerwein-type 1,2-shifts did not meet

  提出了两种途径，允许选择性裂解标​​题化合物中的 Cl/C8b 键。当尝试对杂环化氮杂双环[4.2.0]辛烷进行还原脱苄基化时，偶然发现了第一个反应。它产生了一个八元内酰胺环（偶氮烷）。第二个转变依赖于合理设计的 1,2-重排反应，引入该反应是因为试图诱导经典的 Wagner-Meerwein 型 1,2-转变没有成功。该反应，即反苯甲酸重排，允许将杂环化羟基环丁烷羧酸盐转化为相应的环戊二酮（76% 产率）。
• Enantioselective Total Synthesis of the<i>Melodinus</i>Alkaloid (+)-Meloscine
  作者：Philipp Selig、Thorsten Bach

  DOI：10.1002/anie.200800693

  日期：2008.6.23
• Photochemistry of 4-(2‘-Aminoethyl)quinolones:  Enantioselective Synthesis of Tetracyclic Tetrahydro-1a<i>H</i>-pyrido[4‘,3‘:2,3]- cyclobuta[1,2-<i>c</i>] Quinoline-2,11(3<i>H</i>,8<i>H</i>)-diones by Intra- and Intermolecular [2 + 2]-Photocycloaddition Reactions in Solution
  作者：Philipp Selig、Thorsten Bach

  DOI：10.1021/jo0606608

  日期：2006.7.1

  Enantioselective [2 + 2]-photocycloaddition reactions on 4-(2'-aminoethyl) quinolones in solution were studied using the enantiomerically pure complexing agent 1 as source of chirality. The intermolecular reactions of fully N-protected substrates 5a-5c with different 2-alkyl-substituted acrylates 12-15 represent the first systematic study on the diastereoselectivity of their intermolecular [2 + 2]-photocycloadditions to unsymmetrically 1,1-disubstituted olefins (75-91% yield, d.r. = 58/42-95/5). N-Benzylic-protected photoproducts exo-16a/b-19a/b could easily be converted into lactams 20a/b-23a/b by a sequence of Boc deprotection and thermal lactamization (74-98% yield). Identical products 20a-22a were directly accessible by the intramolecular [ 2 + 2]-photocycloaddition of acrylic acid amides 2-4 (41-61% yield). The suitability of both pathways for an enantioselective reaction variant was proven (70-92% ee). Thus, tetracyclic lactams possessing the carbon framework C were obtained with good yields and enantio-selectivities of up to 92% ee in intramolecular reactions. Comparative investigation of both routes showed that quinolone dimerization was the single most decisive factor preventing a complete chirality transfer. Functional group manipulations were successfully conducted with the primary photoproduct exo-17a. Finally, a new and unexpected type of benzylic hydrogen abstraction-radical cyclization reaction was discovered for substrate 5a, which explains the photochemical instability of substrates 2-5 under short wavelength irradiation (lambda = 300 nm).