89-95-2Relevant articles and documents
Experimental and theoretical study of the effect of active-site constrained substrate motion on the magnitude of the observed intramolecular isotope effect for the P450 101 catalyzed benzylic hydroxylation of isomeric xylenes and 4,4'-dimethylbiphenyl
Audergon, Christian,Iyer, Krishna R.,Jones, Jeffrey P.,Darbyshire, John F.,Trager, William F.
, p. 41 - 47 (1999)
The validity of a cytochrome P450 (P450) 101 force field developed previously was tested by comparing to published results from other laboratories the predicted regioselectivity and stereoselectivity of both (R)- and (S)-norcamphor oxidation when the force field was used. Once validated, the force field was used to test the hypothesis that the magnitude of an observed intramolecular isotope effect is a function of the distance between equivalent but isotopically distinct intramolecular sites of oxidative attack. Molecular dynamics simulations and kinetic deuterium isotope effect experiments on benzylic hydroxylation were then conducted for a series of selectively deuterated isomeric xylenes and 4,4'-dimethylbiphenyl with P450 101. The molecular dynamics simulations predicted that the rank order of substrate mobility in the active site of P450 101 was o-xylene > p- xylene > dimethylbiphenyl. The observed isotope effects for the trideutero analogues were 10.6, 7.4, and 2.7, for the o-xylene, p-xylene, and 4,4'- dimethylbiphenyl, respectively. Thus, as the theoretically predicted rates of interchange between the isotopically distinct methyl groups decrease, the observed isotope effect decreases. The agreement between the theoretical predictions and experimental results provides strong support for the distance hypothesis stated above and for the potential of computational analysis to enhance our understanding of protein/small molecule interactions.
CeO2-nanocubes as efficient and selective catalysts for the hydroboration of carbonyl groups
Bhawar, Ramesh,Bose, Shubhankar Kumar,Patil, Kiran S.
supporting information, p. 15028 - 15034 (2021/09/04)
The CeO2-nanoparticle catalysed hydroboration of carbonyl compounds with HBpin (pin = OCMe2CMe2O) is reported to afford the corresponding borate esters in excellent yield. A series of aromatic and aliphatic aldehydes and ketones having synthetically important functional groups were well-Tolerated under mild reaction conditions. Further, chemoselective hydroboration of aldehydes over other reducible functional groups such as ketone, nitrile, hydroxide, alkene, alkyne, amide, ester, nitro, and halides was achieved. Importantly the catalyst can be recycled up to ten runs with slight loss in activity. This journal is
Deoxygenative hydroboration of primary, secondary, and tertiary amides: Catalyst-free synthesis of various substituted amines
An, Duk Keun,Jaladi, Ashok Kumar,Kim, Hyun Tae,Yi, Jaeeun
, (2021/11/17)
Transformation of relatively less reactive functional groups under catalyst-free conditions is an interesting aspect and requires a typical protocol. Herein, we report the synthesis of various primary, secondary, and tertiary amines through hydroboration of amides using pinacolborane under catalyst-free and solvent-free conditions. The deoxygenative hydroboration of primary and secondary amides proceeded with excellent conversions. The comparatively less reactive tertiary amides were also converted to the corresponding N,N-diamines in moderate yields under catalyst-free conditions, although alcohols were obtained as a minor product.
Sodium Aminodiboranate, a New Reagent for Chemoselective Reduction of Aldehydes and Ketones to Alcohols
Wang, Jin,Guo, Yu,Li, Shouhu,Chen, Xuenian
supporting information, p. 1104 - 1108 (2021/05/25)
Sodium aminodiboranate (NaNH 2(BH 3) 2, NaADBH) is a new member of the old borane family, which exhibits superior performance in chemoselective reduction. Experimental results show that NaADBH can rapidly reduce aldehydes and ketones to the corresponding alcohols in high efficiency and selectivity under mild conditions. There are little steric and electronic effects on this reduction.
