An approximation to the synthesis of several sesquiterpenes from the Guaiane family is described in which the core structure was obtained through a transannular Morita-Baylis-Hillman reaction performed under kinetic resolution. Several manipulations of the obtained MBH adduct have been carried out directed towards the total synthesis of γ-Gurjunene, to the formal synthesis of Clavukerin A, to the synthesis of a non-natural isomer of isoguaiane and to the synthesis of an advanced intermediate in the total synthesis of Palustrol.
Hydrogels are highly hydrophilic polymers that have been used in a wide range of applications. In this study, we prepared PVA–CS/SA–Ca2+ core–shell hydrogels with bilayer space by cross-linking PVA and CS to form a core structure and chelating SA and Ca2+ to form a shell structure to achieve multiple substance loading and multifunctional expression. The morphology and structure of core–shell hydrogels were characterized by scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR). The factors affecting the swelling properties of the hydrogel were studied. The results show that the PVA–CS/SA–Ca2+ hydrogel has obvious core and shell structures. The SA concentration and SA/Ca2+ cross-linking time show a positive correlation with the thickness of the shell structure; the PVA/CS mass ratio affects the structural characteristics of the core structure; and a higher CS content indicates the more obvious three-dimensional network structure of the hydrogel. The optimal experimental conditions for the swelling degree of the core–shell hydrogel were an SA concentration of 5%; an SA/Ca2+ cross-linking time of 90 min; a PVA/CS mass ratio of 1:0.7; and a maximum swelling degree of 50 g/g.
The terpene core structure of suaveolindoles was synthesized through a concise route in a time-economical manner. A scalable synthetic route from pulegone delivered the desired α,β,γ,δ-unsaturated ester in a brief period. By way of Eschenmoser-Claisen rearrangement, carbon side chain moiety at the crowded double-allylic position was introduced stereoselectively.
Herein, the synthesis of a novel adamantanyl-functionalized phthalimide scaffold is demonstrated. The novel compound could be used as a precursor for various synthetic pathways owing to the generic use of adamantane substituents as the driving force for supramolecular interactions with macrocycles and N-substituted phthalimide derivatives as a core structure in numerous drugs. The adamantanyl-functionalized phthalimide scaffold contains bromide groups on the C4 and C5 positions of the benzene ring, effectively allowing further facile modifications of the scaffold. The structure was fully characterized including single-crystal X-ray crystallography. The crystal structure shows an adamantane moiety at an angle of 115.57(7)° to the phthalimide core, hence sterically freeing the adamantane unit for host–guest interactions.
Kinetic Resolution in Transannular Morita-Baylis-Hillman Reaction: An Approximation to the Synthesis of Sesquiterpenes from Guaiane Family
