A convenient transformation of phenols into the corresponding aryl fluorosulfates is presented: the first protocol to completely circumvent direct handling of gaseous sulfuryl fluoride (SOF). The proposed method employs 1,1'-sulfonyldiimidazole as a precursor to generate near-stoichiometric amounts of SOF gas using a two-chamber reactor. With NMR studies, it was shown that this ex situ gas evolution is extremely rapid, and a variety of phenols and hydroxylated heteroarenes were fluorosulfated in good to excellent yields.

The use of copper(0) nanoparticles in the transfer semihydrogenation of alkynes has been investigated as a lead‐free alternative to Lindlar catalysts. A stereo‐selective methodology for the hydrogenation of internal alkynes to the corresponding (Z)‐alkenes in high isolated yields (86% average) has been developed. This green and sustainable transfer hydrogenation protocol relies on non‐noble copper nanoparticles for reduction of both electron‐rich and electron‐deficient, aliphatic‐substituted and aromatic‐ substituted internal alkynes. Polyols, such as ethylene glycol and glycerol, have been proven to act as hydrogen sources, and excellent stereo‐ and chemoselectivity have been observed. Enabling technologies, such as microwave and ultrasound irradiation are shown to enhance heat and mass transfer, whether used alone or in combination, resulting in a decrease in reaction time from hours to minutes.

Application of activated phenol fluorosulfates as substrates in a Pd/NBE mediated sequential alkylation-arylation, commonly known as a Catellani reaction, is presented. These substrates provide a level of complementarity to the commonly used aryl halides and, in combination with a plethora of existing Catellani reaction variations, enable even wider application of this powerful synthetic tool.

Design and synthesis of the second generation C 2 -symmetric 4,8-endo,endo-bis(alkoxy) bicyclo[3.3.1]nona-2,6-diene ligands possessing additional 4,8-exo,exo substituents is reported. The 4,8-exo,exo groups provide a further element for fine-tuning of the ligand structure by enforcing conformational rigidity of the 4,8-endo,endo side chains. Such tetrasubstituted bicyclo [3.3.1] nona-2,6-dienes were employed as steering ligands in the rhodium-catalyzed arylation of cyclic enones with arylboronic acids, providing the corresponding 1,4-addition products in good to excellent yields (69-99 %) and enantioselectivities up to 99 % ee.