10.1016/j.tetlet.2008.05.037
The study presents a rational design of bis(thiourea) cocatalysts to accelerate the Morita–Baylis–Hillman (MBH) reaction, a C–C bond forming reaction known for its sluggishness. By applying electronic structure calculations, the researchers identified key transition states and designed catalysts that could stabilize these states through hydrogen bond recognition of both nucleophile and electrophile. The cocatalysts were synthesized and tested, demonstrating significant acceleration of the MBH reaction between cyclohexenone and 4-fluorobenzaldehyde. The study shows that the designed cocatalysts, particularly one with an o-xylyl bridge, were much more effective than the previously reported bis(thiourea) cocatalyst, nearly tripling the reaction rate. The findings underscore the potential of computational methods in designing organic catalysts that utilize hydrogen bonding for enhanced reactivity.
10.1002/anie.200500466
The study presents the first total synthesis of cavicularin (1), a complex natural product derived from the liverwort Cavicularia densa, which features a strained macrocyclic core with a unique boat-like configuration of one of its arenes. The synthesis involved a radical-induced transannular ring contraction as a key step. Key chemicals used in the study include isovanillin (protected as a dioxolane acetal), 4-fluorobenzaldehyde, sodium borohydride, CBr4/PPh3, neopentyl glycol, DCC, the Herrmann catalyst, DIBALH, and various other reagents for coupling, cyclization, and protection/deprotection steps. These chemicals served to construct and modify the AD and BC ring systems, facilitate cyclization, and ultimately achieve the macrocyclic structure of cavicularin. The study also transformed the macrocyclic precursor into riccardin C, completing the shortest synthesis of this natural product to date.
10.1016/S0040-4020(01)00403-3
The research investigates the sonochemical nucleophilic aromatic substitution reactions on 4-fluorobenzaldehyde with various azacycloalkanes and azoles. The study's purpose was to examine the potential beneficial effects of ultrasound on these reactions, with the aim of improving reaction conditions compared to traditional methods. The conclusions drawn from the research indicate that the application of ultrasonic irradiation significantly enhances the reactions, reducing the reaction time from 5 hours to 15 minutes and increasing the product yields by 15-30%.