Rhodium-Catalyzed O-H Insertion Reactions to (2-Diazo-1,1,3,3,3-pentafluoropropyl)phosphonate: A Convenient Route to
Ita Hajdin1,2, Romana Pajkert1, Haibo Mei3
1School of Science, Constructor University Bremen gGmbH, Campus Ring 1, 28759 Bremen, Germany.
Abstract:
The rhodium(II)-catalyzed insertion of benzyl and alkyl alcohols with 2-diazo-1,1,3,3,3-pentafluoropropylphosphonate unexpectedly afforded fluorinated β-alkoxy vinylphosphonates. The reaction proceeds under mild conditions and shows broad substrate scope. Twenty-four new derivatives were synthesized in moderate to excellent yields with excellent diastereoselectivity (up to 99%). DFT calculations support the proposed mechanism where Z-isomers consistently predominate over E-isomers. For selected tertiary, benzylic, allylic, and acidic alcohols, however, diethyl (1,3,3,3-tetrafluoro-2,2-dihydroxypropyl)phosphonate was obtained as the major product, instead of vinyl phosphonate.
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