A new route to phosphines was developed by a method that features a "pre-join and transform" process that proceeds via acylphosphine intermediates that may be readily prepared from carboxylic acids and disubstituted phosphines. The efficient decarbonylations of these acylphosphines using a nickel catalyst delivered the corresponding phosphines. This method shows that the carboxyl group can play a role similar to halides or triflates for introducing a substituted phosphorus atom on an aromatic ring.

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Metal-catalyzed chain-walking reactions have recently emerged as a powerful strategy to functionalize remote positions in organic molecules. However, a chainwalking protocol for nonconjugated dienes remains scarcely reported, and developments are currently ongoing. In this Communication, a nickel-catalyzed asymmetric hydrocyanation of nonconjugated dienes involving a chain-walking process is demonstrated. The reaction exhibits excellent regio-and chemoselectivity, and a wide range of substrates were tolerated, delivering the products in high yields and enantioselectivities. Deuterium-labeling experiments support the chain-walking process, which involves an iterative b-H elimination and reinsertion processes. Gram-scale synthesis, regioconvergent experiments, and downstream transformations gave further insights into the high potential of this transformation. Scheme 1. State of the art and scope of the current work.

Enantioselective auto‐tandem catalysis represents a challenging yet highlight attractive topic in the field of asymmetric catalysis. In this context, we describe a dual catalytic cycle that merges allylic cyanation and asymmetric hydrocyanation. The one‐pot conversion of a broad array of allylic alcohols into their corresponding 1,3‐dinitriles proceeds in good yield with high enantioselectivity. The products are densely functionalized and can be easily transformed to chiral diamines, dinitriles, diesters, and piperidines. Mechanistic studies clearly support a novel sequential cyanation/hydrocyanation pathway.

Understanding the dissolution of hemicellulose in ionic liquids (ILs) is important in order to explore efficient utilization of ILs for fractionating lignocellulose and extracting hemicellulose. In this study, three ILs, namely 1-butyl-3-methylimidazolium chloride (BmimCl), 1-butyl-3-methylimidazol-ium bromide (BmimBr), and 1-butyl-3-methylimidazolium iodide (BmimI), were used as solvents to dissolve bamboo hemicellulose over the temperature range of 80 °C to 150 °C. Representative hemicellulose with a solubility higher than 9.0 g/100 g IL was regenerated and characterized. The interaction between the hemicellulose and ILs was evaluated using carbon-13 nuclear magnetic resonance. The results showed that the solubility of hemicellulose in the ILs was in the following order: BmimCl > BmimBr > BmimI. Though moderate degradation of the hemicellulose possibly occurred during dissolution, the main chain of the hemicellulose was almost unchanged. The enhanced solubility of the hemicellulose was because of the formation of hydrogen bonds between the hydroxyl proton of the hemicellulose and anion of the ILs.