Thiol esters and boronic acids react to produce ketones under aerobic conditions in the presence of catalytic quantities of a CuI or CuII salt. The reaction occurs at reasonable rates between room temperature and 50 degrees C at neutral pH using thiol esters derived from bulky 2 degrees amides of thiosalicylamides such as those based on N-tert-butyl-2-mercaptobenzamide. In this mechanistically unprecedented reaction system, the carbon-carbon bond formation occurs through templating of the thiol ester and the boronic acid at copper; the system is rendered catalytic in copper under the aerobic conditions.

This paper describes a protocol for the direct comparison of diverse Pt catalysts in the H/D exchange between C 6 H 6 and TFA-d 1 , CD 3 CO 2 D, and TFE-d 3 using turnover number (TON) as a standard metric. An initial survey of Pt complexes, including commercial Pt salts (PtCl 2 , K 2 PtCl 4 ) and Pt chloride complexes containing bidentate and tridentate nitrogen donor ligands, has been conducted. These studies have established that the addition of AgOAc (in TFA-d 1 ) or AgBF 4 (in CD 3 CO 2 D and TFE-d 3 ) displaces the Cl ligands on the Pt precatalyst, which leads to dramatically increased turnover numbers. In general, PtCl 2 and K 2 PtCl 4 provided the fewest turnovers, and species containing bidentate ligands afforded higher turnover numbers than those with tridentate ligands. A diimine Pt complex was found to be a top performing catalyst for H/D exchange with all deuterium sources examined. Interestingly, the relative reactivity of many of the catalysts varied dramatically upon changing the deuterium source, highlighting the need to thoroughly assay potential catalysts under a variety of conditions.

Cationic catalysts in HD: Palladium(II) and platinum(II) complexes of pyridinium‐substituted bipyridine ligands are highly active and stable catalysts for H/D exchange and oxidation of aromatic CH bonds (TONs up to 3200, TOFs up to 0.1 s−1; see scheme, EWG=electron‐withdrawing group, EDG=electron‐donating group).

Cationic catalysts in HD: Palladium(II) and platinum(II) complexes of pyridinium‐substituted bipyridine ligands are highly active and stable catalysts for H/D exchange and oxidation of aromatic CH bonds (TONs up to 3200, TOFs up to 0.1 s−1; see scheme, EWG=electron‐withdrawing group, EDG=electron‐donating group).

This paper describes an efficient synthesis of the cationic platinum complex [(N-CH 3 -bpym)PtCl 2 ] þ (N-CH 3 -bpym=N-methylbipyrimidinium) and evaluation of its catalytic activity in H/D exchange reactions of CH 4 (with D 2 SO 4 ) and benzene (with CF 3 CO 2 D). With both substrates [(N-CH 3 -bpym) PtCl 2 ] þ shows C-H activation reactivity comparable to that of its neutral analogue (bpym)PtCl 2 (bpym=bipyrimidine). The origin of this similar reactivity is proposed to be the in situ formation of the same active catalyst in both cases.