Visible-light-promoted iron-catalyzed C–H functionalization of 1,4-naphthoquinones <i>via</i> oxidative coupling with sulfoximines

Sharma, Alpa; Kour, Harpreet; Kour, Jaspreet; Kamal, Kamal; Sawant, Sanghapal D.

doi:10.1039/d2cc03319d

Cited by 9 publications

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“…Recently, our group has reported a new protocol for the CÀ H functionalization of 1,4-napthoquinones via Fe(III)-catalyzed oxidative coupling with sulfoximines in the presence of visible light. [21] In continuation with this work, we began our studies for the formation of CÀ N bond using sulfoximine and chlorooxime as coupling partners with solely using ethanol as a green solvent at room temperature, offering resulted sulfoximinatedoximes in good to excellent yields.…”

Section: Resultsmentioning

confidence: 99%

Green Approach for N−H Functionalization of Sulfoximines: An Access to Sulfoximinated‐Oxime Conjugates

et al. 2022

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A simple, metal-free, and green approach has been established for NÀ H functionalization of sulfoximines under mild reaction conditions to offer sulfoximinated-oxime conjugates. The reaction works well in EtOH at room temperature and proceeds smoothly without using any base or expensive ligands. This protocol has been applied on various aryl-, heteroaryl-sulfoximines as well as on variety of chloro-oximes. Both the substrates tolerated a wide range of functional groups, resulting in good to excellent yields. It can serve as a directing group in organic synthesis, as a precursor or building block, demonstrating the product's applicability and importance in the field. The applications of the protocol have been demonstrated in the sulfoximination of some natural products. This strategy could be useful in drug discovery or medicinal chemistry for finetuning the physicochemical properties of natural product scaffolds or lead candidates.

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Section: Resultsmentioning

confidence: 99%

Green Approach for N−H Functionalization of Sulfoximines: An Access to Sulfoximinated‐Oxime Conjugates

et al. 2022

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“…Orange solid, mp: 113–115 °C (literature 114–116 °C) . Yield 261 mg (97% at 1.26 mmol scale, reaction time: 0.5 h) using hexane/EtOAc (80:20) as eluent.…”

Section: Methodsmentioning

confidence: 99%

“…Yellow solid, mp: 122–124 °C (literature 122–125 °C) . Yield 300 mg (86% at 1.26 mmol scale, reaction time: 2.0 h) using hexane/EtOAc (80:20) as eluent, [α] D 25 = −13.550 (CHCl 3 , c = 0.001).…”

Section: Methodsmentioning

confidence: 99%

“…Yield 509 mg (95% at 1.26 mmol scale, reaction time: 1.0 h) using hexane/EtOAc (80:20) as eluent. 1 H NMR (500 MHz, CDCl 3 ) δ 8.12 (dd, J = 7.7, 0.8 Hz, 1H), 8.06 (dd, J = 7.7, 0.8 Hz, 1H), 7.74 (td, J = 7.6, 1.2 Hz, 1H), 7.63 (td, J = 7.6, 1.2 Hz, 1H), 5.92 (s, 1H), 5.75 (s, 1H), 3.19 (dd, J = 13.1, 6.9 Hz, 2H), 1.76−1.67 (m, 2H), 1.45−1.38 (m, 2H), 1.27 (brs, 28H), 0.90 (t, J = 6.9 Hz, 3H); 13 72 Yield 261 mg (97% at 1.26 mmol scale, reaction time: 0.5 h) using hexane/EtOAc (80:20) as eluent. 1 H NMR (400 MHz, CDCl 3 ) δ 8.12 (d, J = 7.6 Hz, 1H), 8.07 (d, J = 7.6 Hz, 1H), 7.75 (t, J = 7.5 Hz, 1H), 7.64 (t, J = 7.5 Hz, 1H), 6.03 (s, 1H), 5.91 (ddd, J = 21.7, 10.3, 5.3 Hz, 1H), 5.77 (s, 1H), 5.32 (t, J = 13.0 Hz, 2H), 3.86 (t, J = 4.9 Hz, 2H); 13 78 Yield 270 mg (60% at 1.26 mmol scale, reaction time: 1.0 h) using hexane/EtOAc (90:10) as eluent.…”

Section: ■ Conclusionmentioning

confidence: 99%

“…Three major synthetic strategies have been used for synthesizing 2-amino-1,4-naphthoquinone until now, one of which involves the nucleophilic displacement of the halo group in quinone with amines, ,,, while the second involves a direct 1,4-addition of amines to the quinones, ,, and the third strategy utilized metal catalyzed C–H functionalization of 1,4-naphthoquinone with an amine. ,,, However, the developed methodologies require strong acidic conditions, high temperature, metal catalysts, stoichiometric quantities of oxidant, or a strenuous process and also provide lower yields (Scheme ). ,,,− …”

Section: Introductionmentioning

confidence: 99%

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Blue Light Irradiated Metal-, Oxidant-, and Base-Free Cross-Dehydrogenative Coupling of C(sp²)–H and N–H Bonds: Amination of Naphthoquinones with Amines

2023

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Herein, we report a blue-light-driven amination of C(sp 2)–H bond of naphthoquinones and quinones with the N–H bond of primary and secondary amines for the synthesis of 2-amino-naphthoquinones and 2-amino-quinones. The coupling of naphthoquinones with a wide array of aliphatic, aromatic, chiral, primary, and secondary amines having electron donating (−CH3, −OCH3, −SCH3), withdrawing (−F, −Cl, −Br, −I), and CO2H, −OH, −NH2 groups with acidic protons selectively occurred to afford C–N coupled 2-amino-naphthoquinones in 60–99% yields and hydrogen gas as a byproduct in methanol solvent without using any additional reagents, additives, and oxidant under the blue light irradiation. Mechanistic insight by DFT computation, controlled experiments, kinetic isotopic effect, and substitution effect of the substrates suggest that the reaction proceeds by radical pathway in which naphthoquinone forms a highly oxidizing naphthoquinonyl biradical upon irradiation of blue light (457 nm). Consequently, electron transfer from electron-rich amine to an oxidizing naphthoquinonyl biradical leads to a naphthoquinonyl radical anion and aminyl radical cation, followed by proton transfer and delocalization leading to a carbon-centered naphthoquinonyl radical. The cross-coupling of naphthoquinonyl carbon-centered and aminyl nitrogen radicals forms a C–N bond, with subsequent elimination of hydrogen gas (which was also confirmed by GC-TCD), affording 2-amino-1,4-naphthoquinone under metal-, reagent-, base-, and oxidant-free conditions.

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Direct Functionalization of para‐Quinones: A Historical Review and New Perspectives

Kumar Jha,

Kumar

2024

Eur J Org Chem

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The direct functionalization of quinones has always fascinated research communities due to their biological and redox activities and subsequent application. Quinone motifs play a vital role as precursors for many bioactive compounds and materials; hence, many ingenious methodologies have been elaborated for exploring these units. A significant part of the synthetic strategies towards the functionalized quinones has been achieved by installing substituents on hydroquinones, phenols, or quinone itself by different oxidative coupling reactions via radical pathways with or without the utilization of metal catalysts. The functionalization of simple quinones via direct C‐H bond remains challenging due to their inherited electronic nature and high bond dissociation energy. This review article summarizes the recent advancement made for functionalized quinones through direct functionalization of simple quinones. Our primary focus will be on the synthetic approaches and mechanistic pathways of these reactions that have appeared in the last two decades, along with a short historical importance of the quinone family.

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Visible-light-promoted iron-catalyzed C–H functionalization of 1,4-naphthoquinones via oxidative coupling with sulfoximines

Abstract: A catalytic oxidative addition of sulfoximines to naphthoquinones via its C-H functionalization has been achieved using iron catalytic system, which exhibits good reactivity and high regioselectivity in presence of visible...

Cited by 9 publications

References 33 publications

Green Approach for N−H Functionalization of Sulfoximines: An Access to Sulfoximinated‐Oxime Conjugates

Green Approach for N−H Functionalization of Sulfoximines: An Access to Sulfoximinated‐Oxime Conjugates

Blue Light Irradiated Metal-, Oxidant-, and Base-Free Cross-Dehydrogenative Coupling of C(sp²)–H and N–H Bonds: Amination of Naphthoquinones with Amines

Direct Functionalization of para‐Quinones: A Historical Review and New Perspectives

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Visible-light-promoted iron-catalyzed C–H functionalization of 1,4-naphthoquinones via oxidative coupling with sulfoximines

Abstract: A catalytic oxidative addition of sulfoximines to naphthoquinones via its C-H functionalization has been achieved using iron catalytic system, which exhibits good reactivity and high regioselectivity in presence of visible...

Cited by 9 publications

References 33 publications

Green Approach for N−H Functionalization of Sulfoximines: An Access to Sulfoximinated‐Oxime Conjugates

Green Approach for N−H Functionalization of Sulfoximines: An Access to Sulfoximinated‐Oxime Conjugates

Blue Light Irradiated Metal-, Oxidant-, and Base-Free Cross-Dehydrogenative Coupling of C(sp2)–H and N–H Bonds: Amination of Naphthoquinones with Amines

Direct Functionalization of para‐Quinones: A Historical Review and New Perspectives

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Product

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Blue Light Irradiated Metal-, Oxidant-, and Base-Free Cross-Dehydrogenative Coupling of C(sp²)–H and N–H Bonds: Amination of Naphthoquinones with Amines