1. Grignard-mediated reduction of 2,2,2-trichloro-1-arylethanones
Ali H Essa, Reinner I Lerrick, Eçe Çiftçi, Ross W Harrington, Paul G Waddell, William Clegg, Michael J Hall Org Biomol Chem. 2015 May 28;13(20):5793-803. doi: 10.1039/c5ob00541h. Epub 2015 Apr 23.
2,2,2-Trichloro-1-aryl-ethanones can be reduced by RMgX to the corresponding 2,2-dichloro-1-arylethen-1-olates and trapped with a range of electrophiles resulting in either reduction, reduction/aldol, reduction/Claisen condensation or reduction/aldol-Tishchenko products. In addition we demonstrate that 2,2-dichloro-1-arylethen-1-olates undergo counter-ion controlled Darzens condensations, which can be followed by a thermal rearrangement as a route to 1,3-diaryl-3-chloropropane-1,2-diones.
2. Synergetic DNA-cleaving activities of the metal complexes of a polyether-tethered pyrrole-polyamide dimer
Chun-Qiong Zhou, Yan-Ling Lin, Jin-Xiang Chen, Wen-Hua Chen Chem Biodivers. 2012 Jun;9(6):1125-32. doi: 10.1002/cbdv.201100183.
A simple polyether-tethered pyrrole-polyamide dimer 1 was synthesized in 50% yield from the reaction of 2,2,2-trichloro-1-(1-methyl-4-nitro-1H-pyrrol-2-yl)ethanone with 2,2'-[1,2-ethanediylbis(oxy)]bisethanamine, and fully characterized on the basis of ¹H- and ¹³C-NMR, MS, HR-MS, and IR data. Agarose gel-electrophoresis study of the cleavage of plasmid pBR322 DNA by the complexes of compound 1 with seven metal ions indicated that most of the metal complexes were capable of efficiently cleaving DNA at pH 7.0 and 37°. Among them, the Cu(II) complex exhibited the highest activity, with the maximal catalytic rate constant k(max) and Michaelis constant K(M) being 5.61 h⁻¹ and 7.30 mM, respectively. Spectroscopic, ESI-MS, ethidium-bromide (EB) displacement, and viscosity experiments indicated that compound 1 could form a 1 : 1 complex with Cu(II) ion, and that this complex showed moderate binding affinity toward calf-thymus DNA.
