Exploration of intermediates that enable chemoselective cycloaddition reactions and expeditious construction of fused- or bridged-ring systems is a continuous challenge for organic synthesis. As an intermediate of interest, the oxyallyl cation has been harnessed to synthesize architectures containing seven-membered rings via (4+3) cycloaddition. However, its potential to access five-membered skeletons is underdeveloped, largely due to the thermally forbidden (3+2) pathway. Here, the combination of a tailored precursor and a Pd(0) catalyst generates a Pd-oxyallyl intermediate that cyclizes with conjugated dienes to produce a diverse array of tetrahydrofuran skeletons. The cycloaddition overrides conventional (4+3) selectivity by proceeding through a stepwise pathway involving a Pd-allyl transfer and ring closure sequence. Subsequent treatment of the (3+2) adducts with a palladium catalyst converts the heterocycles to the carbocyclic cyclopentanones.

A novel approach was developed for the synthesis of highly substituted indene derivatives, using an FeCl(3) catalyzed Prins-type cyclization reaction which was further applied in the total synthesis of jungianol and epi-jungianol.

Taking advantage of the C 2-symmetry of the antitumor naturally occurring disorazole B1 molecule, a symmetrical total synthesis was devised with a monomeric advanced intermediate as the key building block, whose three-step conversion to the natural product allowed for an expeditious entry to this family of compounds. Application of the developed synthetic strategies and methods provided a series of designed analogues of disorazole B1, whose biological evaluation led to the identification of a number of potent antitumor agents and the first structure–activity relationships (SARs) within this class of compounds. Specifically, the substitutions of the epoxide units and lactone moieties with cyclopropyl and lactam structural motifs, respectively, were found to be tolerable for biological activities and beneficial with regard to chemical stability.

The divergent synthesis of calothrixins and ellipticines has been accomplished by utilising the one‐pot formation of o‐diacylarenes as a key intermediate through rearrangement of o‐hydroxy ketone monoacyl hydrazones by lead tetraacetate mediated oxidation.

An environmentally benign and highly atom‐economical catalytic method for Friedel–Crafts alkylation and diastereoselective C–O bond formation has been developed. The scope and generality of this reaction is illustrated by the synthesis of chromazonarol, hongoquercins A and B, and their analogues.