Open AccessBimolecular Cross‐Metathesis of a Tetrasubstituted Alkene with Allylic Sulfones
Author(s) -
Sapkota Rishi R.,
Jarvis Jacqueline M.,
Schaub Tanner M.,
Talipov Marat R.,
Arterburn Jeffrey B.
Publication year - 2019
Publication title -
chemistryopen
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.644
H-Index - 29
ISSN - 2191-1363
DOI - 10.1002/open.201800296
Subject(s) - alkene , metathesis , allylic rearrangement , ruthenium , carbene , chemistry , steric effects , combinatorial chemistry , salt metathesis reaction , enyne metathesis , catalysis , reactivity (psychology) , organic chemistry , polymerization , medicine , alternative medicine , pathology , polymer
Exquisite control of catalytic metathesis reactivity is possible through ligand‐based variation of ruthenium carbene complexes. Sterically hindered alkenes, however, remain a generally recalcitrant class of substrates for intermolecular cross‐metathesis. Allylic chalcogenides (sulfides and selenides) have emerged as “privileged” substrates that exhibit enhanced turnover rates with the commercially available second‐generation ruthenium catalyst. Increased turnover rates are advantageous when competing catalyst degradation is limiting, although specific mechanisms have not been defined. Herein, we describe facile cross‐metathesis of allylic sulfone reagents with sterically hindered isoprenoid alkene substrates. Furthermore, we demonstrate the first example of intermolecular cross‐metathesis of ruthenium carbenes with a tetrasubstituted alkene. Computational analysis by combined coupled cluster/DFT calculations exposes a favorable energetic profile for metallacyclobutane formation from chelating ruthenium β‐chalcogenide carbene intermediates. These results establish allylic sulfones as privileged reagents for a substrate‐based strategy of cross‐metathesis derivatization.