[5+2] Cycloaddition of 2‐(2‐Aminoethyl)oxiranes with Alkynes via Epoxide Ring‐Opening: A Facile Access to Azepines

Hu, Chao; Song, Ren‐Jie; Hu, Ming; Yang, Yuan; Li, Jin‐Heng; Luo, Shenglian

doi:10.1002/ange.201604679

Cited by 11 publications

(5 citation statements)

References 87 publications

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“…In another context, Li and Luo have developed hetero [5+ +2] cycloadditions of 2-(2-aminoethyl)oxiranes 164 with alkynes promoted by a combination of FeCl 3 and BF 3 (Et 2 O). [96] The process afforded in the presence of 10 mol% of FeCl 3 and 1 equivalent of BF 3 (Et 2 O) in dichloromethane at room temperature the corresponding 2,3-dihydro-1H-azepines 165 in moderate to good yields (47-73%), as shown in Scheme 46. The reaction featured a broad scope with respect to a wide range of both variously substituted 2-(2-aminoethyl)oxiranes and terminal as well as alkyl-substituted internal alkynes.…”

Section: Miscellaneous [5+ +2] Cycloadditionsmentioning

confidence: 99%

Recent Developments in the [5+2] Cycloaddition

Pellissier

2018

Adv Synth Catal

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The [5+2] cycloaddition allows the synthesis of a diversity of complex highly functionalized seven-membered products in a single step. These cycloadducts can readily be further manipulated synthetically for use in the synthesis of a number of complex natural products and important biologically active products containing seven-membered rings. In addition to the common and highly efficient [5+2] cycloadditions of (oxido)pyrylium and (oxido)pyridinium ions with various p-systems, providing an easy access to a wide range of novel heterocyclic sevenmembered rings exhibiting an oxygen or nitrogen bridge, the metal-catalyzed [5+2] cycloadditions still attract a great attention and have become one of the most popular ways of constructing seven-membered compounds. Among the most important reactions are metal-catalyzed (hetero) [5+2] cycloadditions of vinyl-substituted three-membered rings, rhodium-catalyzed [5+2] cycloadditions of 3-acyloxy-1,4-enynes, and metal-catalyzed [5+2] cycloadditions of ortho-vinylphenols and ortho-vinyl/arylanilines.

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Section: Miscellaneous [5+ +2] Cycloadditionsmentioning

confidence: 99%

Recent Developments in the [5+2] Cycloaddition

Pellissier

2018

Adv Synth Catal

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“…13 C{ 1 H} NMR (101 MHz, CDCl 3 ): δ 168. 8,168.4,160.5 (d,J = 246.4 Hz),145.8,145.1 (d,J = 2.9 Hz),137.0,133.9,133.3,131.5,129.4,128.6,128.3,126.7,125.8,125.5,124.5 (d,J = 8.3 Hz),121.9,116.3 (d,J = 22.7 Hz),100.0,66.3,60.6,60.5,33.9,14.4,14.3. HRMS (ESI-TOF) m/z: calcd for C 28 H 27 FNO 4 [M + H] + , 460.1924; found, 460.1921.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…Zhang and co-workers developed a rhodium(I)-catalyzed intermolecular [5+2]-cycloaddition of vinyl aziridines and alkynes to access nitrogen heterocycles (Scheme b) . The research group of Luo reported an iron/BF 3 ·OEt 2 cocatalyzed intermolecular [5+2]-cycloaddition of 2-(2-aminoethyl)oxiranes with alkynes for producing 2,3-dihydro-1 H -azepines (Scheme c) . Despite the obvious synthetic utility, these approaches remain with a limited substrate scope with regard to both the five-atom units and the alkynes.…”

Section: Introductionmentioning

confidence: 99%

“…7 The research group of Luo reported an iron/BF 3 •OEt 2 cocatalyzed intermolecular [5+2]-cycloaddition of 2-(2-aminoethyl)oxiranes with alkynes for producing 2,3-dihydro-1H-azepines (Scheme 1c). 8 Despite the obvious synthetic utility, these approaches remain with a limited substrate scope with regard to both the five-atom units and the alkynes. Especially, the five-atom units are limited to the protected amines with electron-withdrawing substituents such as Tf, Ts, Ms, or Ns, the common arylamines substrates are very sparse.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Diethyl 1,2- 3,3a,4,7,7epoxybenzo[3,4]cyclobuta [1,2-b]pyrrole-3b,7a-dicarboxylate (8). Yellowish solid, 48 mg, yield 42%.…”

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Temperature-Controlled Divergent Hydroamination Cyclization [2+2]-Cycloaddition Cascade Reactions of Homopropargylic Amines with 2-Butynedioates: Direct Access To Pyrrolo-b-cyclobutene and Dihydro-1H-azepines

Wang

et al. 2019

J. Org. Chem.

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The diversified temperature-controlled hydroamination cyclization cascade reactions of homopropargylic amines and 2-butynedioates were developed for the construction of various pyrrolo-b-cyclobutenes and dihydro-1H-azepines, respectively. This reaction actually involved an intramolecular hydroamination cyclization of homopropargylic amines to give the active dihydropyrroles intermediates, which subsequently underwent [2+2]-cycloaddition with 2-butynedioates to generate the pyrrolo-b-cyclobutenes at no more than 120 °C. Alternatively, the dihydro-1H-azepines were directly produced at 150 °C in the reactions of homopropargylic amines and 2-butynedioates. The application of substrate scope was wide, and the corresponding products were obtained in high to excellent yields.

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Phosphine‐Catalyzed Chemoselective [4+3] Cycloaddition of Alminine Esters and β′‐acetoxy Allenoates for Divergent Synthesis of Azepines

et al. 2019

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Text. A general method for the synthesis of structural diversity and complexity of azepines from aldimine esters and β'-acetoxy allenoates is reported. Under phosphine catalysis, a [4 + 3] cycloaddition for the formation of 1,3-dihydro-2H-azepine-2,2,4-tricarboxylates was achieved with broad substrate scope under mild reactions. A switchable process was given and a variety of important 2,3-dihydrochromeno[4,3-b] azepin-6(1H)-ones were selectively formed when the reaction was performed in the presence of Cs 2 CO 3 and PPh 3 , which involved an intramolecular ester group migration and subsequent lactonization of 1,3-dihydro-2Hazepine-2,2,4-tricarboxylates. Besides easy handle process, high synthetic value of resulting products, it is worth to note that this work showed the novel example of 1,5-ethoxycarbonyl migration.

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[5+2] Cycloaddition of 2‐(2‐Aminoethyl)oxiranes with Alkynes via Epoxide Ring‐Opening: A Facile Access to Azepines

Cited by 11 publications

References 87 publications

Recent Developments in the [5+2] Cycloaddition

Recent Developments in the [5+2] Cycloaddition

Temperature-Controlled Divergent Hydroamination Cyclization [2+2]-Cycloaddition Cascade Reactions of Homopropargylic Amines with 2-Butynedioates: Direct Access To Pyrrolo-b-cyclobutene and Dihydro-1H-azepines

Phosphine‐Catalyzed Chemoselective [4+3] Cycloaddition of Alminine Esters and β′‐acetoxy Allenoates for Divergent Synthesis of Azepines

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