Iron-Mediated Photochemical Anti-Markovnikov Hydroazidation of Unactivated Olefins DOI Creative Commons
Henry Lindner, Willi M. Amberg, Erick M. Carreira

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(41), P. 22347 - 22353

Published: Oct. 9, 2023

Unactivated olefins are converted to alkyl azides with bench-stable NaN3 in the presence of FeCl3·6H2O under blue-light irradiation. The products obtained anti-Markovnikov selectivity, and reaction can be performed mild ambient conditions air moisture. transformation displays broad functional group tolerance, which renders it suitable for functionalization complex molecules. Mechanistic investigations conducted provide insight into hydroazidation reveal role water from iron hydrate as H atom source.

Language: Английский

One-Pot Synthesis of Sulfonamides from Unactivated Acids and Amines via Aromatic Decarboxylative Halosulfonylation DOI

P. Scott Pedersen,

David C. Blakemore,

Gary M. Chinigo

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(39), P. 21189 - 21196

Published: Sept. 20, 2023

The coupling of carboxylic acids and amines to form amide linkages is the most commonly performed reaction in pharmaceutical industry. Herein, we report a new strategy that merges these traditional partners generate sulfonamides, important bioisosteres. This method leverages copper ligand-to-metal charge transfer (LMCT) convert aromatic sulfonyl chlorides, followed by one-pot amination corresponding sulfonamide. process requires no prefunctionalization native acid or amine extends diverse set aryl, heteroaryl, s-rich aliphatic substrates. Further, extend this synthesis (hetero)aryl fluorides, which have found utility as "click" handles chemical probes programmable bifunctional reagents. Finally, demonstrate protocols analogue synthesis.

Language: Английский

Citations

40
Copper-Mediated Dehydrogenative C(sp3)–H Borylation of Alkanes DOI Creative Commons
Ruocheng Sang, Wangyujing Han, Hanwen Zhang

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(28), P. 15207 - 15217

Published: July 6, 2023

Borylations of inert carbon-hydrogen bonds are highly useful for transforming feedstock chemicals into versatile organoboron reagents. Catalysis these reactions has historically relied on precious-metal complexes, which promote dehydrogenative borylations with diboron reagents under oxidant-free conditions. Recently, photoinduced radical-mediated involving hydrogen atom transfer pathways have emerged as attractive alternatives because they provide complimentary regioselectivities and proceed metal-free However, net oxidative processes require stoichiometric oxidants therefore cannot compete the high economy their precious-metal-catalyzed counterparts. Herein, we report that CuCl2 catalyzes radical-mediated, C(sp3)-H alkanes bis(catecholato)diboron This is a result an unexpected dual role copper catalyst, promotes oxidation reagent to generate electrophilic bis-boryloxide acts effective borylating agent in subsequent redox-neutral photocatalytic C-H borylations.

Language: Английский

Citations

38
Benzylic C–H Esterification with Limiting C–H Substrate Enabled by Photochemical Redox Buffering of the Cu Catalyst DOI
Dung L. Golden, Chaofeng Zhang,

Si-Jie Chen

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(17), P. 9434 - 9440

Published: April 21, 2023

Copper-catalyzed radical-relay reactions provide a versatile strategy for selective C-H functionalization; however, with peroxide-based oxidants often require excess substrate. Here, we report photochemical to overcome this limitation by using Cu/2,2'-biquinoline catalyst that supports benzylic esterification limiting Mechanistic studies indicate blue-light irradiation promotes carboxylate-to-copper charge transfer, reducing resting-state CuII CuI, which activates the peroxide generate an alkoxyl radical hydrogen-atom-transfer species. This "photochemical redox buffering" introduces unique sustain activity of Cu catalysts in reactions.

Language: Английский

Citations

37
Light-induced homolysis of copper(ii)-complexes – a perspective for photocatalysis DOI Creative Commons

Alexander Reichle,

Oliver Reiser

Chemical Science, Journal Year: 2023, Volume and Issue: 14(17), P. 4449 - 4462

Published: Jan. 1, 2023

A new kid on the block: Cu( ii ) offers unique possibilities in photocatalysis for generating and stabilizing radicals to promote challenging synthetic transformations.

Language: Английский

Citations

34
Iron-Mediated Photochemical Anti-Markovnikov Hydroazidation of Unactivated Olefins DOI Creative Commons
Henry Lindner, Willi M. Amberg, Erick M. Carreira

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(41), P. 22347 - 22353

Published: Oct. 9, 2023

Unactivated olefins are converted to alkyl azides with bench-stable NaN3 in the presence of FeCl3·6H2O under blue-light irradiation. The products obtained anti-Markovnikov selectivity, and reaction can be performed mild ambient conditions air moisture. transformation displays broad functional group tolerance, which renders it suitable for functionalization complex molecules. Mechanistic investigations conducted provide insight into hydroazidation reveal role water from iron hydrate as H atom source.

Language: Английский

Citations

34