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FeCl3 catalysed regioselective allylation of phenolic substrates with (α-hydroxy)allylphosphonates

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Abstract

Electrophilic allylation of phenolic substrates including salicylaldehydes with (α-hydroxy) allylphosphonates is presented. It is observed that catalytic FeCl3 is sufficient to accomplish the allylation. Interestingly, the reaction led to the formation of allylphosphonates in addition to vinylphosphonates, depending upon the substituent. The vinylphosphonates obtained here are E-isomers. More importantly, the reaction occurred regioselectively with respect to the phenolic substrates. Substituted allylphosphonates are formed when salicylaldehyde or (2-hydroxy-phenyl)arylmethanones are used. Conclusive proof for the formation of allylphosphontates as well as vinylphosphonates has been provided by single crystal X-ray crystallography.

Regioselective allylation of phenolic substrates using phosphono-allyl alcohols was achieved by using even catalytic amounts of FeCl3. Both vinylphosphonates and allylphosphonates are obtained, the ratio depending upon the substrate.

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Acknowledgements

We thank the Department of Science and Technology (DST, New Delhi) and the University Grants Commission (UGC, New Delhi) for financial support. MA and RK thank University Grants Commission (UGC, New Delhi) for fellowship. KCK thanks DST for the J. C. Bose fellowship (No. SR/S2/JCB-53/2010) and UGC for a one-time grant [No. F4-10/2010 (BSR)].

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  1. School of Chemistry, University of Hyderabad, Hyderabad, 500 046, Telangana State, India

    MANDALA ANITHA, RAMESH KOTIKALAPUDI & K C KUMARA SWAMY

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  1. MANDALA ANITHA
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  2. RAMESH KOTIKALAPUDI
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Correspondence to K C KUMARA SWAMY.

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Supplementary Information

Crystallographic data for the structure 7a, 9a and 11b have been deposited with the Cambridge Crystallo- graphic Data Centre as supplementary publication num- ber CCDC 1028043-1028045. Copies of the data can be obtained free of charge, on application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK [fax: +44(1223) 336033 or e-mail: deposit@ccdc.cam.ac.uk]. Copies of 1H/13C/31P NMR spectra are available at www.ias.ac.in/chemsci.

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ANITHA, M., KOTIKALAPUDI, R. & SWAMY, K.C.K. FeCl3 catalysed regioselective allylation of phenolic substrates with (α-hydroxy)allylphosphonates. J Chem Sci 127, 1465–1475 (2015). https://doi.org/10.1007/s12039-015-0903-1

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