Cs2CO3‐Promoted Direct N‐Alkylation: Highly Chemoselective Synthesis of N‐Alkylated Benzylamines and Anilines

Castillo, Juan‐Carlos; Orrego‐Hernández, Jessica; Portilla, Jaime

doi:10.1002/ejoc.201600549

Cited by 73 publications

(44 citation statements)

References 101 publications

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“…Over the decades, the interest in pyrazole derivatives has been significantly increased due to their interesting chemical, physical and biological properties imparting it the status of privileged scaffold. [ 1 ] The pyrazole nucleus involves a five‐membered heterocyclic unit which contains three carbon atoms and two adjacent nitrogens. [ 2 ] Among the azole family, pyrazole is one of the most studied classes of hetereocyclic compounds.…”

Section: Introductionmentioning

confidence: 99%

Exploration of pyrazole based aldo‐x bifunctional building blocks for the synthesis of pyrazole annulated molecular architectures

Sharma

Singh

2020

Journal of Heterocyclic Chem

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Over the last decade, the synthetic chemist's community has attracted attention towards aldo‐x precursors due to their versatility to afforded variety of heterocyclic frameworks. The aldo‐x bifunctional building blocks (AXB3s) contain two or more reactive sites with different reactivity, which may offer new opportunities for the introduction of diversity in core skeleton, which may be of great biological and medicinal relevance. In this context, pyrazole based AXB3s such as 4‐iodopyrazole‐3/5‐carbaldehyde may be explored for achieving pyrazole fused/linked heterocyclic skeletons by employing different organic transformations. Specifically, iodo substituted pyrazoles provide a new platform for the installation of desired pattern via transition‐metal catalyzed approaches. Herein, we have assembled the strategies towards the development of pyrazole substituted and fused molecular architectures by using 4‐iodopyrazole‐3/5‐carbaldehydes and pyrazole C‐3)/C5‐ carbaldehydes. The photophysical data of some fluorescent pyrazole derivatives have also been discussed.

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Section: Introductionmentioning

confidence: 99%

Exploration of pyrazole based aldo‐x bifunctional building blocks for the synthesis of pyrazole annulated molecular architectures

Sharma

Singh

2020

Journal of Heterocyclic Chem

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“…A wide range of homogeneous transition metal-based catalysts accomplishes this domino process and current research focuses on the development of more efficient catalysts for performing the reactions under mild conditions. [4] Current advances in the earth abundant element-based catalysts [6] or transition metal-free highly chemoselective catalytic systems [7] but only a few systems are able to perform asymmetric borrowing hydrogen catalysis. [8] Iridium-based systems, mainly half-sandwich cyclopentadienyl Ir III complexes, are among the most active catalysts in the field of catalytic (transfer) hydrogenation chemistry.…”

Section: Introductionmentioning

confidence: 99%

Mechanistic studies on the N-alkylation of amines with alcohols catalysed by iridium(i) complexes with functionalised N-heterocyclic carbene ligands

Jiménez

Fernández-Tornos

González-Lainez

et al. 2018

Catal. Sci. Technol.

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“…N ‐Benzylbutan‐1‐amine (4e): Colorless liquid (69 mg, 84 % isolated yield). 1 H NMR (600 MHz, CDCl 3 ): δ = 7.32–7.28 (m, 4H), 7.24–7.21 (m, 1H), 3.77 (s, 2H), 2.65–2.57 (m, 2H), 1.48 (p, 3 J HH = 7.4 Hz, 2H), 1.36–1.29 (m, 2H), 0.89 (t, 3 J HH = 7.4 Hz, 3H).…”

Section: Methodsmentioning

confidence: 99%

Nickel(II) Catalyzed Hydroboration: A Route to Selective Reduction of Aldehydes and N‐Allylimines

Hossain

Schmidt

2020

Eur J Inorg Chem

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A cationic [(iminophosphine)nickel(allyl)] + complex was found to be sufficiently electrophilic to activate aldehydes and N-allylimines to undergo hydroboration with pinacolborane (HBpin) under mild reaction conditions. The catalyst displayed excellent selectivity toward aldehydes in the presence of ketones. A wide variety of functional groups were tolerated, includ- [a] I. 1877 ing halogens, NO 2 , CN, OMe, and alkenes for both aldehydes and imines. Electron-rich substrates were found to be significantly more reactive than their electron poor counterparts, a feature that was correlated to their enhanced ability to coordinate to the Lewis acidic nickel center. [40] Colorless liquid (60 mg, 81 % isolated yield). 1 H NMR (600 MHz, CDCl 3 ): δ = 7. 33-7.30 (m, 4H), 7.25-7.22 (m, 1H), 5.92 (ddt, 3 J HH = 17.2, 3 J HH = 10.2, 3 J HH = 6.0 Hz, 1H), 5.19 (dq, 3 J HH = 17.2, 4 J HH = 2 J HH = 1.5 Hz, 1H), 5.10 (dq, 3 J HH = 10.2, 4 J HH = 2 J HH = 1.5 Hz, 1H), 3.78 (s, 2H), 3.27 (dt, 3 J HH = 6.0, 4 J HH = 1.5 Hz, 2H), 1.47 (br s, 1H). 13 C{ 1 H} NMR (151 MHz, CDCl 3 ): δ = 140. 3, 136.9, 128.5, 128.3, 127.1, 116.1, 53.4, 51.9. [30a] Colorless liquid (74 mg, 92 % isolated yield). 1 H NMR (600 MHz, CDCl 3 ): δ = 7.22 (d, 3 J HH = 7.9 Hz, 2H), 7.15 (d, 3 J HH = 7.9 Hz, 2H), 5.94 (ddt, 3 J HH = 17.2, 3 J HH = 10.2, 3 J HH = 6.0 Hz, 1H), 5.20 (dq, 3 J HH = 17.2, 4 J HH = 2 J HH = 1.6 Hz, 1H), 5.12 (dq, 3 J HH = 10.2, 4 J HH = 2 J HH = 1.6 Hz, 1H), 3.76 (s, 2H), 3.28 (dt, 3 J HH = 6.0, 4 J HH = 1.6 Hz, 2H), 2.35 (s, 3H), 1.52 (br s, [41] Colorless liquid (81 mg, 91 % isolated yield). 1 H NMR (600 MHz, CDCl 3 ): δ = 7.24 (d, 3 J HH = 8.3 Hz, 2H), 6.86 (d, 3 J HH = 8.3 Hz, 2H), 5.93 (ddt, 3 J HH = 17.3, 3 J HH = 10.4, 3 J HH = 6.0 Hz, 1H), 5.19 (dq, 3 J HH = 17.3, 4 J HH = 2 J HH = 1.6 Hz, 1H), 5.11 (dq, 3 J HH = 10.4, 4 J HH = 2 J HH = 1.6 Hz, 1H), 3.79 (s, 3H), 3.73 (s, 2H), 3.26 (dt, 3 J HH = 6.0, 4 J HH = 1.6 Hz, 2H), 1.45 (br s, 1H). 13 C{ 1 H} NMR (151 MHz, CDCl 3 ): δ = 158. 7, 136.9, 132.5, 129.5, 116.1, 113.8, 55.4, 52.8, 51.8. N-Benzylprop-2-en-1-amine (2b): N-(4-Methylbenzyl)prop-2-en-1-amine (2c): N-(4-Methoxybenzyl)prop-2-en-1-amine (2d): N-(4-N,N-Dimethylaminobenzyl)prop-2-en-1-amine(2e): [30a] Pale yellow liquid (87 mg, 91 % isolated yield). 1 H NMR (600 MHz, CDCl 3 ): δ = 7.20 (d, 3 J HH = 8.6 Hz, 2H), 6.72 (d, 3 J HH = 8.6 Hz, 2H), 5.94 (ddt, 3 J HH = 16.8, 3 J HH = 10.1, 3 J HH = 6.1 Hz, 1H), 5.19 (dq, 3 J HH = 16.8, 4 J HH = 2 J HH = 1.6 Hz, 1H), 5.10 (dq, 3 J HH = 10.1, 4 J HH = 2 J HH = 1.6 Hz, 1H), 3.70 (s, 2H), 3.27 (dt, 3 J HH = 6.1, 4 J HH = 1.6 Hz, 2H), 2.94 (s, 6H), 1.38 (br s, 1H). 13 C{ 1 H} NMR (151 MHz, CDCl 3 ): δ = 149.9, 136.9, 129.2, 128.2, 115.9, 112.7, 52.8, 51.7, 40.8. N-(4-Fluorobenzyl)prop-2-en-1-amine (2f):[30a] Colorless liquid (71 mg, 86 % isolated yield). 1 H NMR (600 MHz, CDCl 3 ): δ = 7.32-7.27 (m, 2H), 7.04-6.98 (m, 2H), 5.92 (ddt, 3 J HH = 17.1, 3 J HH = 10.2, 3 J HH = 5.9 Hz, 1H), 5.19 (dq, 3 J HH = 17.1, 4 J HH = 2 J HH = 1.4 Hz, 1H), 5.12 (dq, 3 J HH = 10.2, 4 J HH = 2...

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Cs₂CO₃‐Promoted Direct N‐Alkylation: Highly Chemoselective Synthesis of N‐Alkylated Benzylamines and Anilines

Cited by 73 publications

References 101 publications

Exploration of pyrazole based aldo‐x bifunctional building blocks for the synthesis of pyrazole annulated molecular architectures

Exploration of pyrazole based aldo‐x bifunctional building blocks for the synthesis of pyrazole annulated molecular architectures

Mechanistic studies on the N-alkylation of amines with alcohols catalysed by iridium(i) complexes with functionalised N-heterocyclic carbene ligands

Nickel(II) Catalyzed Hydroboration: A Route to Selective Reduction of Aldehydes and N‐Allylimines

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