Highly dispersed palladium chloride catalysts locked in triphenylphosphine-functionalized knitting aryl network polymers (KAPs) are developed and exhibit excellent activity under mild conditions in the Suzuki-Miyaura cross-coupling reactions of aryl chlorides in aqueous media. This work highlights that the microporous polymers not only play the role of support materials, but also protect the Pd species from aggregation and precipitation, hence, positively effect the catalysis activity.

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A highly diastereoselective and enantioselective Cu(II)/SaBOX-catalyzed [2 + 2] cycloaddition of methylidenemalonate and multisubstituted alkenes was developed to furnish optically active cyclobutanes in high yields with >99/1 dr and up to >99% ee. By application of the newly developed method, the total synthesis of (+)-piperarborenine B was completed in eight steps from methylidenemalonate and olefin in 17% overall yield with >99/1 dr and 99% ee.