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Ring‐Closing Olefin Metathesis Catalyzed by Well‐Defined Vanadium Alkylidene Complexes
Author(s) -
Belov Dmitry S.,
Tejeda Gabriela,
Tsay Charlene,
Bukhryakov Konstantin V.
Publication year - 2021
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.202005438
Subject(s) - phosphine , chemistry , catalysis , amide , ring opening metathesis polymerisation , metathesis , medicinal chemistry , ring closing metathesis , acyclic diene metathesis , ether , hydride , olefin fiber , ethylene , vanadium , polymer chemistry , organic chemistry , polymerization , metal , polymer
Abstract Vanadium‐based catalysts have shown activity and selectivity in ring‐opening metathesis polymerization of strained cyclic olefins comparable to those of Ru, Mo, and W catalysts. However, the application of V alkylidenes in routine organic synthesis is limited. Here, we present the first example of ring‐closing olefin metathesis catalyzed by well‐defined V chloride alkylidene phosphine complexes. The developed catalysts exhibit tolerance to various functional groups, such as an ether, an ester, a tertiary amide, a tertiary amine, and a sulfonamide. The size and electron‐donating properties of the imido group and the phosphine play a crucial role in the stability of active intermediates. Reactions with ethylene and olefins suggest that both β‐hydride elimination of the metallacyclobutene and bimolecular decomposition are responsible for catalyst degradation.