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Rhodium‐Catalyzed Oxidative C–H Activation/Cyclization for the Synthesis of Phosphaisocoumarins and Phosphorous 2‐Pyrones
Author(s) -
Park Youngchul,
Seo Jungmin,
Park Sangjune,
Yoo Eun Jeong,
Lee Phil Ho
Publication year - 2013
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201302652
Subject(s) - chemistry , annulation , catalysis , rhodium , yield (engineering) , alkyne , oxidative phosphorylation , ketone , metalation , medicinal chemistry , selectivity , organic chemistry , combinatorial chemistry , biochemistry , materials science , metallurgy
Rhodium‐catalyzed cyclization of phosphinic acids and phosphonic monoesters with alkynes has been developed. The oxidative annulation proceeds with complete conversion of phosphinic acid derivatives and allowed the atom‐economic preparation of useful phosphaisocoumarins with high yield and selectivity. The reaction is tolerant of extensive substitution on the phosphinic acid, phosphonic monoester and alkyne, including halides, ketone, and hydroxyl groups as substituents. Furthermore, we found that alkenylphosphonic monoesters proceed to give a wide range of phosphorus 2‐pyrones through oxidative annulation with alkynes. Mechanistic studies revealed that CH bond metalation was the rate‐limiting step.