Synthesis of <i>N</i>-aryl amines enabled by photocatalytic dehydrogenation

Kim, Jungwon; Kim, Siin; Choi, Geunho; Lee, Geun Seok; Kim, Dong‐Hyeok; Choi, Jungkweon; Ihee, Hyotcherl; Hong, Soon Hyeok

doi:10.1039/d0sc04890a

Cited by 17 publications

(10 citation statements)

References 84 publications

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“…The oxidation of 1a was observed at +1.42 V versus SCE using cyclic voltammetry (CV) (Figure S1). On the anode, the single-electron oxidation of 1a generates the corresponding radical cation 1a •+ , in which the high acidity of α-H causes sequential H abstraction and deprotonation to provide radical intermediate I . According to DFT calculations, the homolytic N–O bond cleavage in intermediate I proceeds smoothly to generate key iminyl radical II through TS1 (Δ G ⧧ = 10.49 kcal/mol).…”

mentioning

confidence: 98%

Complementary Reactivity in Selective Radical Processes: Electrochemistry of Oxadiazolines to Quinazolinones

Hwang

Cho

2021

Org. Lett.

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Electrochemistry has recently emerged as a sustainable approach for efficiently generating radical intermediates utilizing eco-friendly electric energy. An electrochemical process was developed to transform 1,2,4-oxadiazolines under mild conditions. The electrochemical N−O bond cleavage at a controlled oxidation potential led to the selective synthesis of quinazolinone derivatives that could not be obtained by photocatalytic radical processes, indicating complementary reactivities in radical processes. The electrochemical reaction pathways were fully revealed by density functional theory-based investigations.

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confidence: 98%

Complementary Reactivity in Selective Radical Processes: Electrochemistry of Oxadiazolines to Quinazolinones

Hwang

Cho

2021

Org. Lett.

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“…No. 103-32-2] Synthesized according to the general procedure and purified by column chromatography (hexane/EtOAc, 95:5), in 40% yield ( 32 [CAS Reg. No.…”

Section: Paper Synthesismentioning

confidence: 99%

“…The organic layer was dried over Na 2 SO 4 and concentrated to obtain crude product which was purified by column chromatography (EtOAc/hexane) to afford the desired product 3. 32 [CAS Reg. No.…”

Section: Paper Synthesismentioning

confidence: 99%

Regio- and Stereoselective (SN2) N-, O-, C- and S-Alkylation Using Trialkyl Phosphates

Banerjee¹,

Hattori²,

Yamamoto³

2021

Synthesis

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Bimolecular nucleophilic substitution (S N 2) is one of the most known fundamental reactions in organic chemistry to generate new molecules from two molecules. In principle, a nucleophile attacks from the back side of an alkylating agent having a suitable leaving group, most commonly using a halide. However, alkyl halides are expensive, very harmful, toxic and not so stable which makes them problematic for laboratory use. In contrast, trialkyl phosphates are cheap, readily accessible, stable at room temperature, under air, and are easy to handle but rarely used as alkylating agents in organic synthesis. Here, we describe a mild, straightforward and powerful method for nucleophilic alkylation of various nucleophiles such as N-, O-, C- and S- using readily available trialkyl phosphate. The reaction proceeds smoothly with excellent yield and quantitative yield in many cases and covers a wide range of substrates. Further, the rare stereoselective transfer of secondary alkyl groups has been achieved with inversion of configuration of chiral centers (up to >99% ee).

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“…6,7 When the photocatalytic dehydrogenation reaction is performed in an oxygen atmosphere, unexpected side reactions and deep oxidation may arise. 8 Therefore, photocatalytic synthesis of imines via the dehydrogenation reaction of amines under an inert atmosphere environment is greatly desired because it does not have the aforementioned disadvantages.…”

Section: Introductionmentioning

confidence: 99%

“…Compared with these well-established methodologies, the photocatalytic dehydrogenation of primary amines to imines is an environmentally benign and cost-effective route to the direct transformation of amines to imines under ambient conditions . The photocatalytic dehydrogenation reaction can be realized under both an oxygen atmosphere and an oxidant-free environment. , When the photocatalytic dehydrogenation reaction is performed in an oxygen atmosphere, unexpected side reactions and deep oxidation may arise . Therefore, photocatalytic synthesis of imines via the dehydrogenation reaction of amines under an inert atmosphere environment is greatly desired because it does not have the aforementioned disadvantages.…”

Section: Introductionmentioning

confidence: 99%

Sandwich-Structured Hybrid of NiCo Nanoparticles-Embedded Carbon Nanotubes Grafted on C₃N₄ Nanosheets for Efficient Photodehydrogenative Coupling Reactions

Chen

Sun

et al. 2022

ACS Appl. Mater. Interfaces

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Exploring cheap and efficient hybrid catalysts offers exciting opportunities for enhancing the performance of photocatalysts in the green organic synthesis field. Herein, a facile and effective approach is designed for the synthesis of a sandwich-structured hybrid in which NiCo bimetallic nanoparticles are embedded in the tip of nitrogen-doped carbon nanotubes (N-CNTs) grafted on both sides of a nitrogen deficient C3N4 (Nv-C3N4) nanosheet for photodehydrogenative coupling reactions. Such a brand-new type of sandwich-structured hybrid comprises Nv-C3N4 nanosheets and surrounding N-CNTs embedded with NiCo nanoparticles at their tips. Remarkably, the resultant hybrid exhibits integrated functionalities, abundant active sites, enhanced visible light absorption, and excellent interfacial charge transfer ability. As a result, the optimized NiCo@N-CNTs@Nv-C3N4 photocatalyst shows significantly improved photodehydrogenative coupling performance of amines to imines compared to the control single-metal-based catalysts (Ni@N-CNTs@Nv-C3N4 and Co@N-CNTs@Nv-C3N4). The mechanistic investigation through experimental and computational study demonstrates that, compared with single-metal-based hybrids, the NiCo bimetallic hybrid exhibits stronger amine adsorption and weaker photogenerated hydrogen atom adsorption, thus promoting the dehydrogenative activation of primary amines and fast generation of imines. This work presents a promising insight for designing and preparing efficient photocatalysts to trigger organic synthesis in high yields.

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Synthesis of N-aryl amines enabled by photocatalytic dehydrogenation

Abstract: The synergy of SET, HAT, and BET enables a visible-light induced catalytic dehydrogenation for the synthesis of N-aryl amines.

Cited by 17 publications

References 84 publications

Complementary Reactivity in Selective Radical Processes: Electrochemistry of Oxadiazolines to Quinazolinones

Complementary Reactivity in Selective Radical Processes: Electrochemistry of Oxadiazolines to Quinazolinones

Regio- and Stereoselective (SN2) N-, O-, C- and S-Alkylation Using Trialkyl Phosphates

Sandwich-Structured Hybrid of NiCo Nanoparticles-Embedded Carbon Nanotubes Grafted on C₃N₄ Nanosheets for Efficient Photodehydrogenative Coupling Reactions

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Synthesis of N-aryl amines enabled by photocatalytic dehydrogenation

Abstract: The synergy of SET, HAT, and BET enables a visible-light induced catalytic dehydrogenation for the synthesis of N-aryl amines.

Cited by 17 publications

References 84 publications

Complementary Reactivity in Selective Radical Processes: Electrochemistry of Oxadiazolines to Quinazolinones

Complementary Reactivity in Selective Radical Processes: Electrochemistry of Oxadiazolines to Quinazolinones

Regio- and Stereoselective (SN2) N-, O-, C- and S-Alkylation Using Trialkyl Phosphates

Sandwich-Structured Hybrid of NiCo Nanoparticles-Embedded Carbon Nanotubes Grafted on C3N4 Nanosheets for Efficient Photodehydrogenative Coupling Reactions

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Sandwich-Structured Hybrid of NiCo Nanoparticles-Embedded Carbon Nanotubes Grafted on C₃N₄ Nanosheets for Efficient Photodehydrogenative Coupling Reactions