A magnetically recoverable chiral rhodium catalyst exhibited excellent catalytic activity and enantioselectivity in asymmetric transfer hydrogenation of aromatic ketones in aqueous medium, which could be recovered easily via a small magnet and used repetitively ten times without obviously affecting its enantioselectivity.

For over half a century, thousands of tons of triphenylphosphine oxide Ph3P(O) have been produced every year from the chemical industries as a useless chemical waste. Here we disclose efficient transformations of Ph3P(O) with cheap resource-abundant metallic sodium finely dispersed in paraffin oil. Ph3P(O) can be easily and selectively transformed to three reactive organophosphorus intermediates—sodium diphenylphosphinite, sodium 5H-benzo[b]phosphindol-5-olate and sodium benzo[b]phosphindol-5-ide—that efficiently give the corresponding functional organophosphorus compounds in good yields. These functional organophosphorus compounds are difficult to prepare but highly industrially useful compounds. This may allow Ph3P(O) to be used as a precious starting material for highly valuable phosphorus compounds.

The challenging transamidation of unactivated tertiary amides has been accomplished via cooperative acid/iodide catalysis. Most crucially, the method provides a novel manifold to re-route the reactivity of unactivated N,N-dialkyl amides through reactive acyl iodide intermediates, thus reverting the classical order of reactivity of carboxylic acid derivatives. This method provides a direct route to amide-to-amide bond interconversion with excellent chemoselectivity using equivalent amounts of amines. The combination of acid and iodide has been identified as the essential factor to activate the amide CÀ N bond through electrophilic catalytic activation, enabling the production of new desired transamidated products with wide substrate scope of both unactivated amides and amines, including late-stage functionalization of complex APIs (> 80 examples). We anticipate that this powerful activation mode of unactivated amide bonds will find broadranging applications in chemical synthesis.

The direct C-H arylation and acylation of azoles with carboxylic acids were achieved through Pd/Cu cooperative catalysis. A various biaryls and biaryl ketones were selectively produced in good to high...