Head-to-tail peptide macrocyclisations are significantly improved, as measured by isolated yields, reaction rates and product distribution, by substitution of one of the backbone amide CO bonds with an oxetane ring.

The lithiation/borylation-protodeboronation of a homoallyl carbamate was applied to the synthesis of (+)-sertraline and (+)-indatraline. Due to the presence of the alkene, significant modifications of the methodology were required (use of 12-crown-4, TMSCl, H(2)O), or a solvent switch to CHCl(3), to achieve high yields and high selectivities.

A continuous-flow method for the regioselective arylation of fluoroarenes and fluoropyridines has been developed. The telescoped procedure reported here consists of a three-step metalation, zincation, and Negishi cross-coupling sequence, providing efficient access to a variety of functionalized 2-fluorobiaryl products. Precise temperature control of the metalation step, made possible by continuous-flow technology, allowed for the efficient preparation of the arylated products in high yields and short residence times. Additionally, several examples of the regioselective arylation of benzotrifluoride derivatives are also provided.

Highly hindered benzylic carbamates have been reacted with hindered boronic esters to give tertiary boronic esters with very high diastereo- and enantiocontrol and the methodology has been applied to otherwise difficult-to-access molecules.