Regiospecific α-arylation of diverse carbonyl compounds using an organobismuth transporter
- 1Department of Chemistry, University of Chicago, Chicago, IL USA
- 2Department of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, CA USA
Abstract
The α-arylation of carbonyl compounds is a cornerstone transformation in the synthesis of pharmaceuticals and natural products. Despite decades of efforts using transition metal, main-group and photoredox strategies, a general and practical α-arylation method with broad substrate scope has remained elusive. Here we show that 9-bismatriptycene (BisTrip), a rigid, shackled form of triphenylbismuth, functions as a universal aryl group transporter, enabling controlled and regiospecific α-arylation of diverse ketones, allowing the formation of sterically demanding quaternary centres and incorporation of iodoaryl units. BisTrip is readily loaded with aryl groups by a one-pot procedure using arylboronic acids to give Aryl-BisTrip and, after transferring the aryl to the enolate, is recovered quantitatively. Arylation of lithium enolates proceeds within seconds even at −78 °C and shows high fidelity in a memory-of-chirality experiment. Computations support a low barrier for C−C bond formation and account for the observed axial selectivity, establishing BisTrip as a practical platform for α-arylation.
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BibTeX
@article{li2026regiospecific,
title = {{Regiospecific α-arylation of diverse carbonyl compounds using an organobismuth transporter}},
author = {Li Li and Filippo Carpaneto and Pan-Pan Chen and K. N. Houk and Viresh H. Rawal},
journal = {Nature Chemistry},
year = {2026},
month = aug,
doi = {10.1038/s41557-026-02231-5},
url = {https://doi.org/10.1038/s41557-026-02231-5},
note = {CC BY 4.0},
}
RIS
TY - JOUR
TI - Regiospecific α-arylation of diverse carbonyl compounds using an organobismuth transporter
AU - Li Li
AU - Filippo Carpaneto
AU - Pan-Pan Chen
AU - K. N. Houk
AU - Viresh H. Rawal
PY - 2026
DA - 2026/08/18
JO - Nature Chemistry
DO - 10.1038/s41557-026-02231-5
UR - https://doi.org/10.1038/s41557-026-02231-5
AB - The α-arylation of carbonyl compounds is a cornerstone transformation in the synthesis of pharmaceuticals and natural products. Despite decades of efforts using transition metal, main-group and photoredox strategies, a general and practical α-arylation method with broad substrate scope has remained elusive. Here we show that 9-bismatriptycene (BisTrip), a rigid, shackled form of triphenylbismuth, functions as a universal aryl group transporter, enabling controlled and regiospecific α-arylation of diverse ketones, allowing the formation of sterically demanding quaternary centres and incorporation of iodoaryl units. BisTrip is readily loaded with aryl groups by a one-pot procedure using arylboronic acids to give Aryl-BisTrip and, after transferring the aryl to the enolate, is recovered quantitatively. Arylation of lithium enolates proceeds within seconds even at −78 °C and shows high fidelity in a memory-of-chirality experiment. Computations support a low barrier for C−C bond formation and account for the observed axial selectivity, establishing BisTrip as a practical platform for α-arylation.
SN - 1755-4330
SN - 1755-4349
ER -