6305-18-6Relevant articles and documents
Photoenzymatic Hydrogenation of Heteroaromatic Olefins Using ‘Ene’-Reductases with Photoredox Catalysts
Biegasiewicz, Kyle F.,Black, Michael J.,Chung, Megan M.,Hyster, Todd K.,Meichan, Andrew J.,Nakano, Yuji,Sandoval, Braddock A.,Zhu, Tianyu
supporting information, p. 10484 - 10488 (2020/04/29)
Flavin-dependent ‘ene’-reductases (EREDs) are highly selective catalysts for the asymmetric reduction of activated alkenes. This function is, however, limited to enones, enoates, and nitroalkenes using the native hydride transfer mechanism. Here we demonstrate that EREDs can reduce vinyl pyridines when irradiated with visible light in the presence of a photoredox catalyst. Experimental evidence suggests the reaction proceeds via a radical mechanism where the vinyl pyridine is reduced to the corresponding neutral benzylic radical in solution. DFT calculations reveal this radical to be “dynamically stable”, suggesting it is sufficiently long-lived to diffuse into the enzyme active site for stereoselective hydrogen atom transfer. This reduction mechanism is distinct from the native one, highlighting the opportunity to expand the synthetic capabilities of existing enzyme platforms by exploiting new mechanistic models.
I-Pr2NMgCl·LiCl Enables the Synthesis of Ketones by Direct Addition of Grignard Reagents to Carboxylate Anions
Colas, Kilian,Dos Santos, A. Catarina V. D.,Mendoza, Abraham
supporting information, (2019/10/08)
The direct preparation of ketones from carboxylate anions is greatly limited by the required use of organolithium reagents or activated acyl sources that need to be independently prepared. Herein, a specific magnesium amide additive is used to activate and control the addition of more tolerant Grignard reagents to carboxylate anions. This strategy enables the modular synthesis of ketones from CO2 and the preparation of isotopically labeled pharmaceutical building blocks in a single operation.
Site-selective c-h acylation of pyridinium derivatives by photoredox catalysis
Jung, Sungwoo,Lee, Hyeonyeong,Moon, Yonghoon,Jung, Hoi-Yun,Hong, Sungwoo
, p. 9891 - 9896 (2019/10/14)
A strategy for visible-light-induced site-selective C-H acylation of pyridinium salts was developed by employing N-methoxy-or N-aminopyridinium salts, offering a powerful synthetic tool for accessing highly valuable C2- A nd C4-acylated pyridines. The met
