A preparative synthesis of an inwardly directed phosphoramidite-Au complex is described and a description of some of its catalytic performance. The molecular structure was determined by crystallographic analysis, which disclosed that the phosphoramidite ligand points “out” and places the complexed Au “in”. We investigated its catalytic activities and found that the inwardly directed Au is surrounded by three inert walls that provide new opportunities for supramolecular catalysis and study of reactive intermediates.

A preparative synthesis of an inwardly oriented phosphoramidite-Au dinuclear resorcinarene cavitand complex is described, including a description of potent catalytic abilities. The cavitand structure was determined by crystallographic analysis, which revealed that the phosphoramidite P–N bonds point outside placing the two Au atoms inside. We explored the catalytic proclivity of the cavitand and found that it effeciently catalyzes selective and direct dimerization of terminal alkynes to afford conjugated enynes. Mixed dimerizations give rise to chemoselective products, and macrocyclization by intramolecular dimerization are both trademark capabilities of the method.

The direct access to (Z)-(1-bromo-2-chloro-2-arylvinyl)triisopropylsilane through formal addition of BrCl to triisopropylsilyl ethynylarene was explored. BrCl was generated in situ from commercially available TMSCl and N-bromosuccinimide. This simple protocol enabled highly efficient regio- and stereoselective bromochlorination, bis-bromination, and bis-chlorination of the triple bond on a gram scale in the syn mode. It thus provided a potentially diverse scaffold for adaptable preparation of differently all-carbon tetrasubstituted olefins.

One-step synthesis of vicinal bromoiodoenamides from ynamides through IBr addition is described. Two types of IBr were used: commercially available IBr, and in situ generated IBr. This simple protocol enables highly efficient regio- and stereoselective iodobromination of the triple bond on a gram scale in anti-mode, and provides a potentially diverse scaffold for preparation of tetrasubstituted olefins.

Cavitands endowed with in- and outwardly directed allylsilanes are described; epoxidation reactions of the allyl groups with meta-chloroperbenzoic acid are included. The synthesis of introverted and extroverted allylsilanes tethered to triquinoxaline-spanned resorcinarenes was successfully achieved. Competitive epoxidation experiments between the two isomers disclosed that the introverted allyl was more reactive than the extroverted allyl, despite a clearly congested nuisance: the vase-formed cavity would actively stabilize the reaction process.