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Transannular COM July 27th.pdf (1.13 MB)

Catalytic, Transannular Carbonyl-Olefin Metathesis Reactions

preprint
revised on 28.07.2019, 16:21 and posted on 29.07.2019, 16:33 by Paul Riehl, Daniel Nasrallah, Corinna Schindler
A new class of Lewis acid-catalyzed carbonyl-olefin metathesis reactions is described that complements existing protocols for related ring-closing, ring-opening, and intermolecular transformations. These transannular carbonyl-olefin metathesis reactions rely on FeCl3 as an inexpensive Lewis acid catalyst and are mechanistically distinct from previously developed protocols for ring closing, ring-opening and intermolecular metathesis. Specifically, carbonyl-ene and carbonyl-olefin metathesis reaction paths are competing to ultimately favor metathesis as the thermodynamic product. Importantly, we show that distinct Lewis acid catalysts are able to differentiate between these pathways to enable the selective formation of transannular carbonyl-ene or carbonyl-olefin metathesis products thus providing a valuable approach to the molecular editing of naturally occurring complex molecules. Additionally, these results are expected to enable further advances in catalyst design for carbonyl-olefin metathesis to ultimately develop efficient and high-yielding catalytic carbonyl olefination reactions.

Funding

NIH R01-GM118644

History

Email Address of Submitting Author

psriehl@umich.edu

Institution

University of Michigan

Country

United States

ORCID For Submitting Author

0000-0003-3810-1627

Declaration of Conflict of Interest

No conflict of interest

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