Tungsten‐based bimetallic catalysts M–W/AC (M=Ru, Pt, and Pd; AC=activated carbon) exhibited high activity and selectivity in the hydrogenolysis of typical α‐O‐4 model compounds and deconstruction of lignin feedstock for the production of aromatic chemicals. Synergy effect was observed between tungsten and noble‐metal species, which on the one hand modulated the hydrogenolysis activity of tungsten and improved the activity of catalyst, and on the other hand suppressed overhydrogenation that avoided the formation of cycloalkanes. The conversion of α‐O‐4 model compounds with different substituents showed that electronic effects play an important role in stabilizing the reaction intermediates, and the electron‐donating methoxy group on the aromatic ring accelerated the hydrogenolysis efficiency. Solvent effect was another factor that determined hydrogenolysis efficiency; dipolar aprotic solvents such as n‐hexane provided the high yields of target aromatics. In the conversion of realistic lignins, the bimetallic catalyst showed excellent activity not only in α‐O‐4 cleavage but also in the hydrogenolysis of other major linkages such as β‐O‐4 and β−β between aromatic units, so that a high yield of liquid oil was obtained from lignin.
An efficient synthesis of substituted benzenes via a base-catalyzed [3 + 3] aerobic oxidative aromatization of α,β-unsaturated carbonyl compounds with dimethyl glutaconate was reported. All the reactions were carried out under mild, metal-free conditions to afford the products in high to excellent yields with molecular oxygen as the sole oxidant and water as the sole byproduct. Furthermore, a more convenient tandem [3 + 2 + 1] aerobic oxidative aromatization reaction was developed through the in situ generation of the α,β-unsaturated carbonyl compounds from aldehydes and ketones.
A new strategy for the rapid construction of functionalized reduced indoles starting from activated methylene isocyanides and 1,5-dielectrophilic 5-oxohepta-2,6-dienoates (and their equivalents) through a [5+1] annulation-isocyanide cyclization cascade under basic conditions has been developed. This strategy allows the synthesis of polysubstituted dihydroindolones and tetrahydroindolones in high to excellent yields under extremely mild conditions in a single step.
A new benzannulation strategy that proceeds via a regiospecific [4 + 2] cycloaddition of readily available cyclobutenones and active methylene ketones has been developed. On the basis of this strategy, persubstituted phenols/anilines with up to six different functional groups on the benzene ring were synthesized in a single step. In addition, a series of acridine derivatives were prepared in excellent yield from persubstituted phenols/anilines.
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