Unprecedented Control of Selectivity in Nickel-Catalyzed Hydrophosphorylation of Alkynes: Efficient Route to Mono- and Bisphosphonates
Received: February 3, 2014; Published online: March 3, 2014Dedicated to the memory of Z. A. Starikova.Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201400123.Abstract: A unique nickel-based catalytic system wasdeveloped where the direction of the hydrophos-phorylation reaction can be controlled by varyingthe catalyst loading. A flexible one-pot access to vi-nylmonophosphonates and alkylbisphosphonates wasdemonstrated using simple starting materials in anatom-economic reaction without any specific solventsor ligands. Monitoring of the reaction mechanismwith joint NMR and MS studies revealed key infor-mation about the reaction intermediates. The syn-thetic scope of the developed catalytic system wasexplored and the utility of the synthesized productsfor the fire protection of cotton materials was dem-onstrated.Keywords: alkynes; homogeneous catalysis; nickel;phosphorylation; selectivity