Direct Aziridination of Nitroalkenes Affording <i>N</i>-Alkyl-<i>C</i>-nitroaziridines and the Subsequent Lewis Acid Mediated Isomerization to β-Nitroenamines

Hao, Feiyue; Asahara, Haruyasu; Nishiwaki, Nagatoshi

doi:10.1021/acs.orglett.7b02724

Cited by 15 publications

(11 citation statements)

References 45 publications

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“…Indeed, when trans-β-nitrostyrene (28a) is treated with propylamine and NCS in the presence of cesium carbonate, trans-1-propyl-2-nitroaziridine (29a) is formed in 72% yield (Scheme 10). 26 Interestingly, the reaction using cis-β-nitrostyrene (28a') also affords trans-aziridine (29a), which indicates that both products are formed via common intermediate (30…”

Section: Direct Synthesis Of N-alkylated Aziridines From Nitroalkenesmentioning

confidence: 99%

“…Other 3-nitro-2-quinolones also undergo aziridination (Table 3). Moreover, a strong electron-withdrawing nitro group is not necessary for an efficient aziridination; the yield of aziridine (26) increases as the electron density of the benzene ring decreases. This tendency indicates that the acidity of the hydrogen at the 4-position is crucial for determining the reaction path: an acidic hydrogen favors the elimination of nitrous acid affording amino-chlorinated product (25), while intramolecular nucleophilic substitution proceeds much faster with a less acidic hydrogen, facilitating aziridination predominantly.…”

Section: Scheme 7 Resonance Structures Of the Meqone Frameworkmentioning

confidence: 99%

“…In particular, their decomposition is accelerated during silica gel column chromatography, which indicates that they are highly reactive under acidic conditions. When aziridines (29) are treated with tin(II) chloride, β-aryl-β-nitroenamines (70) are diastereoselectively formed in the Z-configuration due to an intramolecular hydrogen bond(Table 9) 26.…”

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Chemistry of Nitroaziridines

Nishiwaki¹,

Hao²

2019

HETEROCYCLES

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This review article introduced synthetic procedures for the preparation of structurally diverse nitroaziridines. In addition, this article also summarized reactivity of nitroaziridines caused by the inherent strain and high electrophilicity of the small ring. These properties facilitate their use as a functionalized building blocks in synthetic and medicinal chemistry. INTRODUCTION Aziridines are an important class of nitrogen-containing heterocycles that can be found in a number of biologically active compounds, such as mitomycin, porfiromycin, and azinomycin. 1 Due to the inherent ring strain and high electrophilicity, they undergo ring-opening reactions with various nucleophiles to produce a wide range of nitrogen-containing compounds such as amino acids, amino sugars and alkaloids. 2 In contrast to epoxides, aziridines can be readily metalated and reacted with electrophiles, 3 leading to a broader range of functionalized derivatives, which serve as versatile building blocks in organic synthesis. 1,4 Indeed, a substantial number of functionalized aziridines have been transformed into useful products such as an HIV protease inhibitor, 5 communesin, 6 ceramide, 7 and oseltamivir 8 via rearrangement, cycloaddition, and ring expansion reactions. 4 Among various functional groups, the nitro group is highly attractive in synthetic chemistry owing to the strongly electron-withdrawing ability and its versatility for obtaining diverse functionalized compounds by chemical conversion. 9 Considering the above features, we focused our attention on nitroaziridines, which are important synthetic intermediates. 10 Hence, the chemistry of nitroaziridines is reviewed here. This article is dedicated to Professor Tohru Fukuyama on the occasion of his 70th birthday.

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Section: Direct Synthesis Of N-alkylated Aziridines From Nitroalkenesmentioning

confidence: 99%

Section: Scheme 7 Resonance Structures Of the Meqone Frameworkmentioning

confidence: 99%

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Chemistry of Nitroaziridines

Nishiwaki¹,

Hao²

2019

HETEROCYCLES

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“…On the other hand, nitroalkenes possess an electron-deficient double bond, and hence, they serve as an excellent Michael acceptor and dienophile [12][13][14][15][16][17][18][19]. When β-nitrostyrene (1, Ar = Ph) is subjected to the Diels-Alder reaction, a C2 unit possessing a nitro group and an aryl group at the vicinal position is incorporated into the products.…”

Section: One-pot and Metal-free Synthesis Of 3-arylated-4-nitrophenolmentioning

confidence: 99%

One-pot and metal-free synthesis of 3-arylated-4-nitrophenols via polyfunctionalized cyclohexanones from β-nitrostyrenes

Asahara

Hiraishi

Nishiwaki

2020

Beilstein J. Org. Chem.

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β-Nitrostyrenes underwent a Diels–Alder reaction with Danishefsky’s diene to afford cyclohexenes together with the corresponding hydrolyzed products, 3-arylated-5-methoxy-4-nitrocyclohexanones. When the reaction was conducted in the presence of water, the cyclohexenes were efficiently hydrolyzed into cyclohexanones. Subsequent aromatization by heating the cyclohexanone with a catalytic amount of iodine in dimethyl sulfoxide gave 3-arylated-4-nitrophenols. The reaction of nitrostyrenes with Danishefsky’s diene could be conducted in one pot to directly afford the corresponding nitrophenols. Moreover, a heteroaryl group, e.g., a thienyl group could be introduced into the nitrophenol framework.

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“…On the other hand, nitroalkenes possess an electron-deficient double bond, and hence, they serve as an excellent Michael acceptor and dienophile. [12][13][14][15][16][17][18][19] When -nitrostyrene 1 is subjected to the Diels-Alder reaction, a C2 unit possessing a nitro group and an aryl group at the vicinal position is incorporated into the products. This unique reactivity prompted us to probe the synthesis of 3-arylated 4-nitrophenols 5 by the Diels-Alder reaction of nitrostyrenes 1 with Danishefsky's diene 2 (the trimethylsiloxy group of the diene can be converted to a phenolic hydroxy group by hydrolysis), followed by oxidation and aromatization of the obtained cyclohexanone 4 (Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

One-Pot and Metal-Free Synthesis of 3-Arylated 4-Nitrophenols via Polyfunctionalized Cyclohexanones from β-Nitrostyrenes

Asahara¹,

Hiraishi²,

Nishiwaki³

2020

Preprint

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β-Nitrostyrenes underwent the Diels-Alder reaction with Danishefsky’s diene to afford cyclohexenes together with the corresponding hydrolyzed products, 3-arylated 5-methoxy-4-nitrocyclohexanones. When the reaction was conducted in the presence of water, the cyclohexenes were efficiently hydrolyzed into cyclohexanones. Subsequent aromatization by heating the cyclohexanone with a catalytic amount of iodine in dimethyl sulfoxide gave 3-arylated 4-nitrophenols. The reaction of nitrostyrenes with Danishefsky’s diene could be conducted in one-pot to directly afford the corresponding nitrophenols. Moreover, a heteroaryl group such as a thienyl group could be introduced into the nitrophenol framework.

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Direct Aziridination of Nitroalkenes Affording N-Alkyl-C-nitroaziridines and the Subsequent Lewis Acid Mediated Isomerization to β-Nitroenamines

Cited by 15 publications

References 45 publications

Chemistry of Nitroaziridines

Chemistry of Nitroaziridines

One-pot and metal-free synthesis of 3-arylated-4-nitrophenols via polyfunctionalized cyclohexanones from β-nitrostyrenes

One-Pot and Metal-Free Synthesis of 3-Arylated 4-Nitrophenols via Polyfunctionalized Cyclohexanones from β-Nitrostyrenes

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