The direct carbonylation of 1,3-butadiene offers the potential for a more cost-efficient and environmentally benign route to industrially important adipic acid derivatives. However, owing to the complex reaction network of regioisomeric carbonylation and isomerization pathways, a selective practical catalyst for this process has thus far proven elusive. Here, we report the design of a pyridyl-substituted bidentate phosphine ligand (HeMaRaphos) that, upon coordination to palladium, catalyzes adipate diester formation from 1,3-butadiene, carbon monoxide, and butanol with 97% selectivity and 100% atom-economy under industrially viable and scalable conditions (turnover number > 60,000). This catalyst system also affords access to a variety of other di- and triesters from 1,2- and 1,3-dienes.

The first catalyst for the alkoxycarbonylation of gem-difluoroalkenes is described. This novel catalytic transformation proceeds in the presence of Pd(acac) 2 /1,2-bis((ditert-butylphosphan-yl)methyl)benzene (btbpx) (L4)a nd allows for an efficient and straightforwarda ccess to ar ange of difluoromethylated esters in high yields and regioselectivities.T he synthetic utility of the protocol is showcased in the practical synthesis of aC yclandelate analogue using this methodology as the key step.

A new silver-catalyzed oxyfluorination of unactivated alkenes using commercially available Selectfluor as the fluorine source is presented. This method provides a new access to 5-(fluoromethyl)-4,5-dihydroisoxazoles, and represents a new example of alkene 1,2-difunctionalization by simultaneously forming two new carbon-heteroatom bonds.

In the presence of phosphine oxides, specifically triphenylphosphine oxide (P14), the cobalt-catalyzed hydroformylation of olefins takes place under mild conditions compared to traditional processes. It is shown that the addition of P14 dramatically improves the preactivation of the classic cobalt precatalyst, thus saving time and energy. In addition, we show that anisole, a solvent with a high sustainability rank, can be used advantageously in such processes.

The stereoselective synthesis of conjugated dienes was realized for the first time via Pd-catalyzed alkoxycarbonylation of easily available 1,3-diynes.K ey to success is the utilization of the specific ligand 1,1'-ferrocenediyl-bis(tertbutyl(pyridin-2-yl)phosphine) (L1), whicha llows this novel transformation to proceed at room temperature.Arange of 1,2,3,4-tetrasubstituted conjugated dienes are obtained in this straightforwarda ccess in high yields and selectivities.T he synthetic utility of the protocol is showcased in the concise synthesis of several important intermediates for construction of natural products rac-cagayanin, rac-galbulin, rac-agastinol, and cannabisin G. Scheme 1. Selective synthesis of 1,2,3,4-tetrasubstituted conjugated dienes:C hallenges and new method.