We show that by judicious choice of substituents at the 2- and 7-positions of pyrene, the frontier orbital order of pyrene can be modified, giving enhanced control over the nature and properties of the photoexcited states and the redox potentials. Specifically, we introduced a julolidine-like moiety and Bmes (mes=2,4,6-Me C H ) as very strong donor (D) and acceptor (A), respectively, giving 2,7-D-π-D- and unsymmetric 2,7-D-π-A-pyrene derivatives, in which the donor destabilizes the HOMO-1 and the acceptor stabilizes the LUMO+1 of the pyrene core. Consequently, for 2,7-substituted pyrene derivatives, unusual properties are obtained. For example, very large bathochromic shifts were observed for all of our compounds, and unprecedented green light emission occurs for the D/D system. In addition, very high radiative rate constants in solution and in the solid state were recorded for the D-π-D- and D-π-A-substituted compounds. All compounds show reversible one-electron oxidations, and Jul Pyr exhibits a second oxidation, with the largest potential splitting (ΔE=440 mV) thus far reported for 2,7-substituted pyrenes. Spectroelectrochemical measurements confirm an unexpectedly strong coupling between the 2,7-substituents in our pyrene derivatives.
Modular 1,2,3-triazoles enabled iron-catalyzed CH arylations with broad scope. The novel triazole-based bidentate auxiliary is easily accessible in a highly modular fashion and allowed for user-friendly iron-catalyzed C(sp(2) )H functionalizations of arenes and alkenes with excellent chemo- and diastereoselectivities. The versatile iron catalyst also proved applicable for challenging C(sp(3) )H functionalizations, and proceeds by an organometallic mode of action. The triazole-assisted CH activation strategy occurred under remarkably mild reaction conditions, and the auxiliary was easily removed in a traceless fashion. Intriguingly, the triazole group proved superior to previously used auxiliaries.
Site-selective ruthenium(II)-catalyzed direct arylation of amides was achieved through CH cleavages with modular auxiliaries, derived from easily accessible 1,2,3-triazoles. The triazolyldimethylmethyl (TAM) bidentate directing group was prepared in a highly modular fashion through copper(I)-catalyzed 1,3-dipolar cycloaddition and allowed for ruthenium-catalyzed CH arylations on arenes and heteroarenes, as well as alkenes, by using easy-to-handle aryl bromides as the arylating reagents. The triazole-assisted CH activation strategy was found to be widely applicable, to occur under mild reaction conditions, and the catalytic system was tolerant of important electrophilic functionalities. Notably, the flexible triazole-based auxiliary proved to be a more potent directing group for the optimized ruthenium(II)-catalyzed direct arylations, compared with pyridyl-substituted amides or substrates derived from 8-aminoquinoline.
We report here a manganese-catalyzed C-H methylation reaction of considerable substrate scope, using MeMgBr, a catalytic amount of MnCl·2LiCl, and an organic dihalide oxidant. The reaction features ambient temperature, low catalyst loading, typically 1%, high catalytic turnover reaching 5.9 × 10, and no need for an extraneous ligand and illustrates a unique catalytic use of simple manganese salts for C-H activation, which so far has relied on catalysis by manganese carbonyls.
Phenolic compounds are vast, diverse, ubiquitous and widespread in nature. The biological significance of bioactive phenolic natural secondary metabolites is immense and of high and significant importance. Phenolic compounds are known to exhibit various biological activities such as antimicrobial, antioxidant and anti-inflammatory properties. This book chapter begins with classification of phenolic compounds in concise manner followed by going through their chemical properties that are essential for their biological activities. Some chemical properties such as acidity and formation of radicals are directly linked with their important and key biological activities such as antioxidant properties. The chapter covers methods and updated techniques of analysis of phenolic compounds. Finally, biosynthesis of such important organic molecules is covered going through some of their current synthesis methods in the laboratory, methods of their synthetic elaboration. Due to the high potential of phenolic compounds for applications in various industries such as pharmaceutical and food industries, the search for the development of efficient methods for their synthesis as well as modern and accurate methods for their detection and analysis will continue.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.