Z‐Retentive Enantioselective Rh‐Catalyzed Hydroarylation of E,Z‐Dienes
- 1Department of Chemistry University of Alberta Edmonton Alberta Canada
Abstract
Metal‐catalyzed additions to alkenes are among the most versatile methods to prepare enantioenriched small molecules. Processes that selectivity functionalize an E‐alkene in the presence of a Z‐alkene remain elusive, however, they would be an attractive approach to access chiral molecules with a remaining group capable of stereospecific functionalization. Here, we report the Z‐retentive enantioselective Rh‐catalyzed hydroarylation of electron‐poor E,Z‐dienes. The reaction gives targets in >95% ee without alkene Z‐to‐E isomerization. The product β‐aryl‐Z‐γ,δ‐unsaturated carbonyl compounds can be readily transformed into polyfunctional products containing multiple adjacent stereocenters in high diastereomeric ratios (≥90:10) via stereospecific alkene functionalizations. Mechanistic studies suggest that Rh‐enolate protonolysis is the turnover‐limiting step, and a selectivity model is developed based on reactivity and kinetic studies with E,E‐dienes and E/Z‐alkenes. DFT studies were used to shed light on the nature of the substrate‐catalyst interactions which likely lead to the observed selectivity. These results may have wide spanning implications for developing new Z‐retentive alkene addition reactions.
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BibTeX
@article{mcnutt2026zretentive,
title = {{Z‐Retentive Enantioselective Rh‐Catalyzed Hydroarylation of E,Z‐Dienes}},
author = {Wesley McNutt and Hima Kozhummal and Abdullah Al‐Mashqbeh and Alex Brown and Rylan J. Lundgren},
journal = {Angewandte Chemie (International Ed. in English)},
year = {2026},
month = sep,
doi = {10.1002/anie.8809022},
url = {https://doi.org/10.1002/anie.8809022},
note = {CC BY-NC-ND 4.0},
}
RIS
TY - JOUR
TI - Z‐Retentive Enantioselective Rh‐Catalyzed Hydroarylation of E,Z‐Dienes
AU - Wesley McNutt
AU - Hima Kozhummal
AU - Abdullah Al‐Mashqbeh
AU - Alex Brown
AU - Rylan J. Lundgren
PY - 2026
DA - 2026/09/26
JO - Angewandte Chemie (International Ed. in English)
DO - 10.1002/anie.8809022
UR - https://doi.org/10.1002/anie.8809022
AB - Metal‐catalyzed additions to alkenes are among the most versatile methods to prepare enantioenriched small molecules. Processes that selectivity functionalize an E‐alkene in the presence of a Z‐alkene remain elusive, however, they would be an attractive approach to access chiral molecules with a remaining group capable of stereospecific functionalization. Here, we report the Z‐retentive enantioselective Rh‐catalyzed hydroarylation of electron‐poor E,Z‐dienes. The reaction gives targets in >95% ee without alkene Z‐to‐E isomerization. The product β‐aryl‐Z‐γ,δ‐unsaturated carbonyl compounds can be readily transformed into polyfunctional products containing multiple adjacent stereocenters in high diastereomeric ratios (≥90:10) via stereospecific alkene functionalizations. Mechanistic studies suggest that Rh‐enolate protonolysis is the turnover‐limiting step, and a selectivity model is developed based on reactivity and kinetic studies with E,E‐dienes and E/Z‐alkenes. DFT studies were used to shed light on the nature of the substrate‐catalyst interactions which likely lead to the observed selectivity. These results may have wide spanning implications for developing new Z‐retentive alkene addition reactions.
SN - 1433-7851
SN - 1521-3773
ER -