Pd/BIPHEPHOS is an Efficient Catalyst for the Pd-Catalyzed S-Allylation of Thiols with High n-Selectivity.

The Pd-catalyzed S-allylation of thiols with stable allylcarbonate and allylacetate reagents offers several advantages over established reactions for the formation of thioethers. We could demonstrate that Pd/BIPHEPHOS is a catalyst system which allows the transition metal-catalyzed S-allylation of thiols with excellent n-regioselectivity. Mechanistic studies showed that this reaction is reversible under the applied reaction conditions. The excellent functional group tolerance of this transformation was demonstrated with a broad variety of thiol nucleophiles (18 examples) and allyl substrates (9 examples), and could even be applied for the late-stage diversification of cephalosporins, which might find application in the synthesis of new antibiotics.

Labeling and Natural Post-Translational Modification of Peptides and Proteins via Chemoselective Pd-Catalyzed Prenylation of Cysteine.

The prenylation of peptides and proteins is an important post-translational modification observed in vivo. We report that the Pd-catalyzed Tsuji-Trost allylation with a Pd/BIPHEPHOS catalyst system allows the allylation of Cys-containing peptides and proteins with complete chemoselectivity and high n/i regioselectivity. In contrast to recently established methods, which use non-native connections, the Pd-catalyzed prenylation produces the natural n-prenylthioether bond. In addition, a variety of biophysical probes such as affinity handles and fluorescent tags can be introduced into Cys-containing peptides and proteins. Furthermore, peptides containing two cysteine residues can be stapled or cyclized using homobifunctional allylic carbonate reagents.

Impacts of surface gold mining on land use systems in Western Ghana.

Land use conflicts are becoming increasingly apparent from local to global scales. Surface gold mining is an extreme source of such a conflict, but mining impacts on local livelihoods often remain unclear. Our goal here was to assess land cover change due to gold surface mining in Western Ghana, one of the world's leading gold mining regions, and to study how these changes affected land use systems. We used Landsat satellite images from 1986-2002 to map land cover change and field interviews with farmers to understand the livelihood implications of mining-related land cover change. Our results showed that surface mining resulted in deforestation (58%), a substantial loss of farmland (45%) within mining concessions, and widespread spill-over effects as relocated farmers expand farmland into forests. This points to rapidly eroding livelihood foundations, suggesting that the environmental and social costs of Ghana's gold boom may be much higher than previously thought.