292825-75-3Relevant articles and documents
Attenuation of London Dispersion in Dichloromethane Solutions
Pollice, Robert,Bot, Marek,Kobylianskii, Ilia J.,Shenderovich, Ilya,Chen, Peter
supporting information, p. 13126 - 13140 (2017/09/26)
London dispersion constitutes one of the fundamental interaction forces between atoms and between molecules. While modern computational methods have been developed to describe the strength of dispersive interactions in the gas phase properly, the importance of inter-and intramolecular dispersion in solution remains yet to be fully understood because experimental data are still sparse in that regard. We herein report a detailed experimental and computational study of the contribution of London dispersion to the bond dissociation of proton-bound dimers, both in the gas phase and in dichloromethane solution, showing that attenuation of inter-and intramolecular dispersive interaction by solvent is large (about 70% in dichloromethane), but not complete, and that current state-of-The-Art implicit solvent models employed in quantum-mechanical computational studies treat London dispersion poorly, at least for this model system.
Benzoyl peroxide promoted radical ortho-alkylation of nitrogen heteroaromatics with simple alkanes and alcohols
Fang, Lei,Chen, Liangshun,Yu, Jianjun,Wang, Limin
, p. 1910 - 1914 (2015/03/18)
A catalytic amount of benzoyl peroxide (BPO)-initiated cross-dehydrogenative coupling reaction of N-iminopyridine ylides with simple alkanes and alcohols leads to the corresponding 2-alkylpyridines with high regioselectivity in moderate to good yields without an additional reduction step to remove the activated group. A catalytic amount of benzoyl peroxide (BPO)-initiated cross-dehydrogenative coupling reaction of N-iminopyridine ylides with simple alkanes and alcohols has been developed. The strategy allowed convenient access to various 2-alkylpyridines in moderate to good yields without an additional reduction step to remove the activated group.
The AZARYPHOS family of ligands for ambifunctional catalysis: Syntheses and use in ruthenium-catalyzed anti-markovnikov hydration of terminal alkynes
Hintermann, Lukas,Dang, Tuan Thanh,Labonne, Aurelie.,Kribber, Thomas,Xiao, Li,Naumov, Pance
supporting information; experimental part, p. 7167 - 7179 (2010/02/28)
The family of AZARYPHOS (aza-aryl-phosphane) phosphane ligands, containing a phosphine unit and sterically shielded nitrogen lone pairs in the ligand periphery, is introduced as a tool for developing ambifunctional catalysis by the metal center and nitrogen lone pairs in the ligand sphere. General synthetic strategies have been developed to synthesize over 25 examples of structurally diverse (6-aryl-2pyridyl)phosphanes (ARPYPHOS), (6alkyl-2-pyridyl)phosphanes (ALPY-PHOS), 4,6-disubsituted l,3-diazin-2ylphosphanes or l,3,5-triazin-2- ylphosphanes, quinazolinylphosphanes, quinolinylphosphanes, and others. The scalable syntheses proceed in a few steps. The incorporation of AZARYPHOS ligands (L) into complexes [RuCp(L)2(MeCN)][PF6] (Cp = cyclopentadieny1)gives catalysts for the anti-Markovnikov hydration of terminal alkynes of the highest known activities. Electronic and steric ligand effects modulate the reaction kinetics over a range of two orders of magnitude. These results highlight the importance of using structurally diverse ligand families in the process of developing cooperative ambifunctional catalysis by a metal and its ligand.
