Jankins TC,
Bell WC,
Zhang Y,
Qin Z.-Y,
Chen JS,
Gembicky M,
Liu P,
*,
Engle KM.
*
University of Pittsburgh and The Scripps Research Institute, La Jolla, USA
Low-Valent Tungsten Redox Catalysis Enables Controlled Isomerization and Carbonylative Functionalization of Alkenes.
Nat. Chem. 2022;
14: 632-639
DOI:
10.1038/s41557-022-00951-y
Key words
tungsten catalysis - alkene functionalization - hydrocarbonylation - redox catalysis
Significance
A tungsten-catalyzed isomerization of terminal alkenes to unactivated internal positions followed by subsequent hydrocarbonylation with CO is reported. This work addresses common challenges associated with the regioselectivity of tandem alkene isomerization/functionalization reactions.
Comment
Experimental and DTF studies were carried out to elucidate the mechanism. Key to this transformation is the six- to seven-coordinate geometry changes present in the W(0)/W(II) redox cycle and the presence of a conformationally flexible directing group that allows for isomerization to take place.
