Achieving Molecular Fluorescent Conversion from Aggregation-Caused Quenching to Aggregation-Induced Emission by Positional Isomerization

In this work, we synthesized a pair of positional isomers by attaching a small electron-donating pyrrolidinyl group at ortho- and para-positions of a conjugated core. These isomers exhibited totally different fluorescent properties. PDB2 exhibited obvious aggregation-induced emission properties. In contrast, PDB4 showed the traditional aggregation-caused quenching effect. Their different fluorescent properties were investigated by absorption spectroscopy, fluorescence spectroscopy, density functional theory calculations and single-crystal structural analysis. These results indicated that the substituent position of the pyrrolidinyl groups affects the twisted degree of the isomers, which further induces different molecular packing modes, thus resulting in different fluorescent properties of these two isomers. This molecular design concept provided a new accurate strategy for designing new aggregation-induced emission luminogens.

Catalytic, contra-Thermodynamic Alkene Isomerization

The positional isomerization of C–C double bonds is a powerful strategy for the interconversion of alkene regioisomers. However, existing methods provide access to thermodynamically more stable isomers from less stable starting materials. Here we report the discovery of a dual catalyst system that promotes contra-thermodynamic positional alkene isomerization under photochemical irradiation, providing access to terminal alkene isomers directly from conjugated, internal alkene starting materials. The utility of the method is demonstrated in the deconjugation of diverse electron rich/poor alkenes and through strategic application to natural product synthesis. Mechanistic studies are consistent with a regiospecific bimolecular homolytic substitution (SH2') mechanism proceeding through an allyl-cobaloxime intermediate.

Cobalt catalyzed isomerization of alkenes

Catalytic isomerization of alkenes is a highly atom-economical approach to upgrade from lower- to higher-value alkenes. Consequently, tremendous attention has been devoted to the development of this transformation, approaches which exploit cobalt-catalysis are particularly attractive. This short review focuses on the cobalt-catalyzed alkene isomerization, including positional isomerization, geometric isomerization and cycloisomerization. Three main types of reaction mechanism have been discussed to help the reader to better understand and make meaningful comparison between the different transformations. 1 Introduction 2 Positional isomerization 3 Geometric isomerization 4 Cycloisomerization 5 Conclusion and Outlook

Discovery and Insight into One-photon and Two-photon Excited ACQ-to-AIE Conversion via Positional Isomerization

Two positional isomers (regioisomers) through changing the substituted position of perylenetetracarboxylic diimide and benzanthrone moieties were designed and synthesized. These two regioisomers exhibit totally different aggregation behaviors. The meta (bay)-substituted...

Selecting Double Bond Positions with a Single Cation- Responsive Iridium Olefin Isomerization Catalyst

<div><div><div><p>The catalytic transposition of double bonds holds promise as an ideal route to alkenes with value as fragrances, commodity chemicals, and pharmaceuticals; yet, selective access to specific isomers is a challenge, requiring independent development of different catalysts for different products. In this work, a single cation-responsive iridium catalyst is developed for the selective production of either of two different internal alkene isomers. In the absence of salts, a single positional isomerization of 1-butene derivatives furnishes 2-alkenes with exceptional regioselectivity and stereoselectivity. The same catalyst, in the presence of Na+, mediates two positional isomerizations to produce 3-alkenes. The synthesis of new iridium pincer-crown ether catalysts based on an aza-18-crown-6 ether proved instrumental in achieving cation-controlled selectivity. Experimental and computational studies guided the development of a mechanistic model that explains the observed selectivity for various functionalized 1-butenes, providing insight into strategies for catalyst development based on non-covalent modifications.</p></div></div></div>

Selecting Double Bond Positions with a Single Cation- Responsive Iridium Olefin Isomerization Catalyst

<div><div><div><p>The catalytic transposition of double bonds holds promise as an ideal route to alkenes with value as fragrances, commodity chemicals, and pharmaceuticals; yet, selective access to specific isomers is a challenge, requiring independent development of different catalysts for different products. In this work, a single cation-responsive iridium catalyst is developed for the selective production of either of two different internal alkene isomers. In the absence of salts, a single positional isomerization of 1-butene derivatives furnishes 2-alkenes with exceptional regioselectivity and stereoselectivity. The same catalyst, in the presence of Na+, mediates two positional isomerizations to produce 3-alkenes. The synthesis of new iridium pincer-crown ether catalysts based on an aza-18-crown-6 ether proved instrumental in achieving cation-controlled selectivity. Experimental and computational studies guided the development of a mechanistic model that explains the observed selectivity for various functionalized 1-butenes, providing insight into strategies for catalyst development based on non-covalent modifications.</p></div></div></div>

Positional Isomerization of Phenylethanoid Glycosides from Magnolia officinalis

Positional isomerization, an inducement leading to instability of phenylethanoid glycosides (PhGs) containing the caffeoyl moiety linked to C-3/4 of the central saccharide, is reported. Magnolosides M, A and F from Magnolia officinalis were found to be transformed into their isomers magnolosides A, D, M and B, respectively, which indicated that PhGs containing the caffeoyl moiety linking to C-3/4 of the central saccharide were unstable, and the caffeoyl group could be transferred to either C-4/3 or C-6 of the central saccharide. In addition, among the factors of temperature, solvent type and exposure time in solvent, temperature was found to play a critical role in initiation of positional isomerization of PhGs. In order to retard this isomerization, the temperature should be lower than 40°C during the final purification stages of PhGs.