Synfacts 2022; 18(09): 0977
DOI: 10.1055/s-0041-1738683
Metals in Synthesis

Tungsten-Catalyzed Alkene Isomerization/Hydrocarbonylative Cyclization

Contributor(s):
Mark Lautens
,
Alexa Torelli
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
 

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.


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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.


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Publication History

Article published online:
18 August 2022

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