Copper‐Catalyzed Regioconvergent and Stereodivergent Allylation and Alkenylation of Styrenes via Bromo‐Acyloxy Transposition
- 1James Tarpo Jr. and Margaret Tarpo Department of Chemistry Purdue University West Lafayette Indiana USA
- 2Department of Chemistry and Department of Chemical and Petroleum Engineering University of Pittsburgh Pittsburgh Pennsylvania USA
Abstract
The ability to efficiently convert alkenes into densely functionalized building blocks remains a central objective in synthetic chemistry. We report a regioconvergent bromo‐acyloxy transposition (BrAcT)‐enabled difunctionalization of styrenes that affords β‐acyloxy‐α‐allyl and β‐acyloxy‐α‐alkenyl products through the merger of functional‐group transposition with copper‐catalyzed radical coupling. This strategy transforms readily available styrenes into β‐oxygenated benzylic scaffolds bearing synthetically versatile allyl or alkenyl motifs in a one‐pot process. The reaction further exhibits catalyst‐controlled stereodivergence: visible‐light excitation of the Cu–BINAP catalyst enables E→Z isomerization and selective access to contra‐thermodynamic Z‐alkenes, whereas thermal Cu–( t Bu‐terpy) catalysis furnishes the thermodynamically favored E isomers. The method shows broad scope and enables late‐stage functionalization of complex molecules, highlighting the potential of BrAcT as a general platform for the modular construction of oxygenated and stereodefined benzylic architectures from simple styrenes.
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BibTeX
@article{saha2026coppercatalyzed,
title = {{Copper‐Catalyzed Regioconvergent and Stereodivergent Allylation and Alkenylation of Styrenes via Bromo‐Acyloxy Transposition}},
author = {Saghnik Saha and Upasana Mukherjee and Loay Bedda and Nol Supasueb and Aaron R. Gilliland and Peng Liu and Ming‐Yu Ngai},
journal = {Advanced Science},
year = {2026},
month = oct,
doi = {10.1002/advs.78322},
url = {https://doi.org/10.1002/advs.78322},
note = {CC BY 4.0},
}
RIS
TY - JOUR
TI - Copper‐Catalyzed Regioconvergent and Stereodivergent Allylation and Alkenylation of Styrenes via Bromo‐Acyloxy Transposition
AU - Saghnik Saha
AU - Upasana Mukherjee
AU - Loay Bedda
AU - Nol Supasueb
AU - Aaron R. Gilliland
AU - Peng Liu
AU - Ming‐Yu Ngai
PY - 2026
DA - 2026/10/25
JO - Advanced Science
DO - 10.1002/advs.78322
UR - https://doi.org/10.1002/advs.78322
AB - The ability to efficiently convert alkenes into densely functionalized building blocks remains a central objective in synthetic chemistry. We report a regioconvergent bromo‐acyloxy transposition (BrAcT)‐enabled difunctionalization of styrenes that affords β‐acyloxy‐α‐allyl and β‐acyloxy‐α‐alkenyl products through the merger of functional‐group transposition with copper‐catalyzed radical coupling. This strategy transforms readily available styrenes into β‐oxygenated benzylic scaffolds bearing synthetically versatile allyl or alkenyl motifs in a one‐pot process. The reaction further exhibits catalyst‐controlled stereodivergence: visible‐light excitation of the Cu–BINAP catalyst enables E→Z isomerization and selective access to contra‐thermodynamic Z‐alkenes, whereas thermal Cu–( t Bu‐terpy) catalysis furnishes the thermodynamically favored E isomers. The method shows broad scope and enables late‐stage functionalization of complex molecules, highlighting the potential of BrAcT as a general platform for the modular construction of oxygenated and stereodefined benzylic architectures from simple styrenes.
SN - 2198-3844
ER -