Site- and enantioselective cross-coupling of saturated N-heterocycles with carboxylic acids by cooperative Ni/photoredox catalysis DOI Creative Commons
Xiaomin Shu,

De Zhong,

Qian Huang

и другие.

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Янв. 9, 2023

Abstract Site- and enantioselective cross-coupling of saturated N -heterocycles carboxylic acids—two the most abundant versatile functionalities—to form pharmaceutically relevant α-acylated amine derivatives remains a major challenge in organic synthesis. Here, we report general strategy for highly site- α-acylation with situ-activated acids. This modular approach exploits hydrogen-atom-transfer reactivity photocatalytically generated chlorine radicals combination asymmetric nickel catalysis to selectively functionalize cyclic α-amino C−H bonds presence benzylic, allylic, acyclic α-amino, α-oxy methylene groups. The mild scalable protocol requires no organometallic reagents, displays excellent chemo-, enantioselectivity, is amenable late-stage diversification, including synthesis previously inaccessible Taxol derivatives. Mechanistic studies highlight exceptional versatility chiral catalyst orchestrating (i) catalytic elimination, (ii) alkyl radical capture, (iii) cross-coupling, (iv) induction.

Язык: Английский

Synthetic Applications of Photocatalyzed Halogen‐Radical Mediated Hydrogen Atom Transfer for C−H Bond Functionalization DOI Creative Commons
Stefano Bonciolini, Timothy Noël, Luca Capaldo

и другие.

European Journal of Organic Chemistry, Год журнала: 2022, Номер 2022(34)

Опубликована: Май 13, 2022

Abstract The opportunity to activate C(sp 3 )−H bonds via homolytic cleavage by means of halogen radicals has long been disregarded in synthetic endeavors due the unpredictable selectivity. Nowadays, photocatalysis established itself as a method choice for generation such reactive intermediates under mild conditions. This Minireview collects recent examples showcasing how photocatalytic manifolds have used tame aggressive Hydrogen Atom Transfer (HAT) purposes. In last section this work, we address site‐selectivity issues posed methodology and show it can be guided through judicious reaction

Язык: Английский

Процитировано

71
Photochemical aerobic oxidation of sulfides to sulfoxides: the crucial role of wavelength irradiation DOI Creative Commons

Elpida Skolia,

Petros L. Gkizis,

Nikolaos F. Nikitas

и другие.

Green Chemistry, Год журнала: 2022, Номер 24(10), С. 4108 - 4118

Опубликована: Янв. 1, 2022

Introducing green and sustainable photochemical aerobic protocols for the oxidation of sulfides to sulfoxides.

Язык: Английский

Процитировано

70
Derivatized Benzothiazoles as Two-Photon-Absorbing Organic Photosensitizers Active under Near Infrared Light Irradiation DOI
Bidyut Kumar Kundu, Guan‐Qun Han, Yujie Sun

и другие.

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(6), С. 3535 - 3542

Опубликована: Фев. 2, 2023

Homogeneous organic photocatalysis typically requires molecular photosensitizers absorbing in the ultraviolet-visible (UV/vis) region, because UV/vis photons possess sufficient energy to excite those one-photon-absorbing desired excited states. However, light irradiation has many potential limitations, especially for large-scale applications, such as low penetration through reaction media, competing absorption by substrates and co-catalysts, incompatibility with bearing light-sensitive functionalities. In fact, these drawbacks can be effectively avoided if near infrared (NIR) utilized drive target reactions. Herein, we report two benzothiazole-derived compounds novel two-photon-absorbing (TPA) photosensitizers, which function under NIR using inexpensive LED source. We demonstrate that judicially modulating donor-π-acceptor-π-donor-conjugated structure containing a bibenzothiazole core imine bridges, excellent two-photon capability region achieved, approaching 2000 GM at 850 nm. Together large quantum yields (∼0.5), TPA exhibit performance driving various O2-involved reactions upon nm, showing great depth, superior blue irradiation. A suite of photophysical computational studies were performed shed on underlying electronic states responsible observed capability. Overall, this work highlights promise developing Ru/Ir-free operative taking advantage mechanism.

Язык: Английский

Процитировано

67
Resurgence and advancement of photochemical hydrogen atom transfer processes in selective alkane functionalizations DOI Creative Commons
Liang Chang, Shun Wang, Qing An

и другие.

Chemical Science, Год журнала: 2023, Номер 14(25), С. 6841 - 6859

Опубликована: Янв. 1, 2023

The selective functionalization of alkanes has long been recognized as a prominent challenge and an arduous task in organic synthesis. Hydrogen atom transfer (HAT) processes enable the direct generation reactive alkyl radicals from feedstock have successfully employed industrial applications such methane chlorination process,

Язык: Английский

Процитировано

66
Site- and enantioselective cross-coupling of saturated N-heterocycles with carboxylic acids by cooperative Ni/photoredox catalysis DOI Creative Commons
Xiaomin Shu,

De Zhong,

Qian Huang

и другие.

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Янв. 9, 2023

Abstract Site- and enantioselective cross-coupling of saturated N -heterocycles carboxylic acids—two the most abundant versatile functionalities—to form pharmaceutically relevant α-acylated amine derivatives remains a major challenge in organic synthesis. Here, we report general strategy for highly site- α-acylation with situ-activated acids. This modular approach exploits hydrogen-atom-transfer reactivity photocatalytically generated chlorine radicals combination asymmetric nickel catalysis to selectively functionalize cyclic α-amino C−H bonds presence benzylic, allylic, acyclic α-amino, α-oxy methylene groups. The mild scalable protocol requires no organometallic reagents, displays excellent chemo-, enantioselectivity, is amenable late-stage diversification, including synthesis previously inaccessible Taxol derivatives. Mechanistic studies highlight exceptional versatility chiral catalyst orchestrating (i) catalytic elimination, (ii) alkyl radical capture, (iii) cross-coupling, (iv) induction.

Язык: Английский

Процитировано

56