期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 61, 期 8, 页码 -出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202113827
关键词
Cycloisomerizations; gem-Hydrogenation; NMR Spectroscopy; Rearrangements; Ruthenium Carbenes
资金
- Max-Planck-Gesellschaft
In this study, a new hydrogenation reaction transformation was reported, where propargyl alcohol derivatives were converted to cyclopentene products using [(CpRu)-Ru-X(MeCN)(3)]PF6 as catalyst. It was also discovered that rearrangements leading to other organic compounds could occur when the transient carbene carried appropriate substituents.
gem-Hydrogenation of propargyl alcohol derivatives with [(CpRu)-Ru-X(MeCN)(3)]PF6 (Cp-X=substituted cyclopentadienyl) as catalysts affords cationic pianostool ruthenium carbene complexes which are so electrophilic that they attack a tethered olefin to furnish cyclopentene products; cyclopropanation or metathesis do not compete with this novel transformation. If the transient carbenes carry appropriate propargylic substituents, however, they engage in ([2,3]-sigmatropic) rearrangements to give enol esters (carbonates, carbamates, sulfonates) or alkenyl halides. Both pathways are unprecedented in the vast hydrogenation literature. The proposed mechanistic scenarios are in line with labeling experiments and spectroscopic data; most notably, PHIP NMR spectroscopy (PHIP=parahydrogen induced polarization) provides compelling evidence that the reactions are indeed triggered by highly unorthodox gem-hydrogenation events.
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