55573-14-3Relevant academic research and scientific papers
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.
Difunctionalization of Alkenylpyridine N-Oxides by the Tandem Addition/Boekelheide Rearrangement
Xun, Xudong,Zhao, Man,Xue, Jianzhong,Hu, Tao,Zhang, Ming,Li, Guofeng,Hong, Liang
supporting information, p. 8266 - 8269 (2019/10/16)
A convenient and efficient approach for the difunctionalization of alkenylpyridine N-oxides through the tandem addition/Boekelheide rearrangement has been developed. The C-O and C-X (S, O, Cl) bonds are constructed simultaneously at the α- and β-positions under mild reaction conditions in 100% atom economy, which complements previously reported α- or β-functionalizations.
Iron-Catalyzed Aerobic Oxidation of (Alkyl)(aryl)azinylmethanes
Sterckx, Hans,Sambiagio, Carlo,Lemière, Filip,Tehrani, Kourosch Abbaspour,Maes, Bert U. W.
supporting information, p. 1564 - 1570 (2017/08/11)
An iron-catalyzed aerobic oxidation of (alkyl)(aryl)azinylmethanes has been developed leading to tertiary alcohols in moderate to good yields. Hock rearrangement was identified as a major side reaction leading to a complex mixture of undesired products. Addition of thiourea sometimes allows inhibiting this side reaction and steers the reaction towards the desired products.
Friedel-Crafts hydroxyalkylation through activation of a carbonyl group using AlBr3: An easy access to pyridyl aryl/heteroaryl carbinols
Harikrishnan, Adhikesavan,Selvakumar, Jayaraman,Gnanamani, Elumalai,Bhattacharya, Suman,Ramanathan, Chinnasamy Ramaraj
supporting information, p. 563 - 567 (2013/04/10)
Aromatic electrophilic substitution of aromatic/electron rich heteroaromatic compounds with AlBr3 activated aldehydes/ketone to afford pyridyl aryl/heteroaryl or diaryl carbinols is described. The strong electron donating group dictates the regiochemical outcome of the product.
