4-Pyrazolyl-1,2,3-triazoles can be readily synthesized in a one-pot fashion and moderate yield by employing a consecutive four-component process consisting of a sequentially Pd-Cu-catalyzed alkynylation-cyclocondensation-desilylation-CuAAC process. Most distinctly, (triisopropylsilyl)butadiyne is employed as a four-carbon building block in this one-pot de novo formation of both heterocyclic moieties.

We report a simple and efficient one‐pot synthesis of 1,2‐diketones by concatenation of two Pd/Cu‐catalyzed processes: Pd0/CuI‐catalyzed Sonogashira coupling of terminal alkynes with aryl (pseudo)halides furnishes internal alkynes, which are directly transformed by PdII/CuII‐catalyzed Wacker‐type oxidation with DMSO and oxygen as dual oxidants to furnish 1,2‐diketones. With this efficient, catalyst economical process, various aryl iodides and triflates are efficiently transformed in high yields into symmetrically and unsymmetrically substituted 1,2‐diketones with various functional groups. This process can be readily extended to a consecutive one‐pot synthesis of quinoxalines in a diversity‐oriented fashion.

A new highly diastereoselective synthesis of chiral α-substituted allylboronic esters, based on a one-pot, three-step cascade, is presented. The palladium- and acid-cocatalyzed reaction cascade involves a desilylation of a TBS-protected allylic alcohol, borylation, and addition of an allyl group to an aldehyde. Herein we present the first application of a TBS-protected allylic alcohol in a palladium-catalyzed borylation/allylation reaction.

A sequentially Pd/Cu‐catalyzed alkynylation‐desilylation‐alkynylation‐cycloisomerization (ADAC) process in the sense of a consecutive three‐component reaction using TIPS‐butadiyne as a four carbon building block gives a rapid and efficient access to 2,2′‐biindolyls in a one‐pot fashion. This facile entry to unsymmetrically substituted title compounds has been employed in a concise two‐step synthesis of the alga alkaloid tjipanazole I.