First Hydrophosphination Using a Germanium Precatalyst

  • Author:
  • Published: 13 October 2020
  • Copyright: Wiley-VCH GmbH
  • Source / Publisher: Chemical Communications/Royal Society of Chemistry
  • Associated Societies: Royal Society of Chemistry (RSC), UK
thumbnail image: First Hydrophosphination Using a Germanium Precatalyst

Transition-metal catalysts are widely used in organic synthesis. Using catalysts based on main-group elements instead could help to reduce costs and environmental impact for many reactions. Germanium catalysis, for example, can be used for the polymerization of lactide or the hydroboration of carbonyls. However, transformations catalyzed by germanium are still rare overall, and extending this limited range would be useful.

Ruth L. Webster and colleagues, University of Bath, UK, have developed the first hydrophosphination protocol that uses a germanium precatalyst. The precatalyst, [GeCl{N(SiMe3)2}3] (pictured), was prepared by a reaction of GeCl4 with NaN(SiMe3)2. It was then used in reactions of diphenylphosphine with styrenes or internal alkynes at room temperature. The desired hydrophosphination products were obtained in good to excellent yields with anti-Markovnikov selectivity.

The team proposes a reaction mechanism that involves the formation of a germanium-(tris)phosphido complex of the type GeCl(PPh2)3 as the active catalyst. The alkene then inserts into Ge–P bonds and forms alkyl intermediates, and protonolysis gives the final product. According to the researchers, this work could be a basis for the development of other germanium-catalyzed hydrofunctionalization reactions.



Article Views: 2955

Sign in Area

Please sign in below

Additional Sign In options

Please note that to comment on an article you must be registered and logged in.
Registration is for free, you may already be registered to receive, e.g., the newsletter. When you register on this website, please ensure you view our terms and conditions. All comments are subject to moderation.

Article Comments - To add a comment please sign in

If you would like to reuse any content, in print or online, from, please contact us first for permission and consult our permission guidance prior to making your request

Follow on Facebook Follow on Twitter Follow on YouTube Follow on LinkedIn Follow on Instagram RSS Sign up for newsletters

Magazine of Chemistry Europe (16 European Chemical Societies) published by Wiley-VCH