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Green, Palladium‐Catalyzed Synthesis of Benzylic H ‐Phosphinates from Hypophosphorous Acid and Benzylic Alcohols
Author(s) -
Coudray Laëtitia,
Montchamp JeanLuc
Publication year - 2008
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.200800581
Subject(s) - chemistry , xantphos , catalysis , palladium , substrate (aquarium) , organic chemistry , medicinal chemistry , ethanol , oceanography , geology
Benzylic alcohols cross‐couple directly with concentrated H 3 PO 2 by using Pd/xantphos (1 or 2 mol‐%). Depending on the substrate, DMF at 110 °C or t ‐AmOH at reflux with a Dean–Stark trap can be used. A broad range of benzylic alcohols react successfully to give moderate to good yields of the products. The preparation of other organophosphorus compounds (phosphinic and phosphonic acids) is also demonstrated. Asymmetric reaction with ( R )‐1‐(2‐naphthyl)ethanol provids the corresponding H ‐phosphinic acid in 77 % ee . The methodology provides a green, PCl 3 ‐free route to benzylic‐ H ‐phosphinic acids.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)