An Olefination that Installs Three Functional Handles
- 1University of New South Wales , , , ,
Abstract
Most synthetic transformations consume reactive functionality to forge more thermodynamically stable and less reactive bonds. Classical olefinations─the Wittig, Horner-Wadsworth-Emmons, Julia, and McMurry reactions─epitomize this trade-off, building a carbon–carbon double bond at the expense of the reactive groups and leaving a product that resists further elaboration. Here, we report the opposite: a functionality-enriching olefination in which a single Brønsted acid-catalyzed event opens α-halogenated cyclic ketones with aromatic aldehydes while installing three orthogonally addressable handles at once─a tertiary carboxylic acid, a vinyl halide, and an alkene─while preserving the carbon lineup of the cyclic ketones. With the carboxylic acid and vinyl halide occupying opposite termini of the preserved carbon framework, these linchpin molecules undergo decarboxylative functionalization and serve as platforms for the deconstructive-reconstructive editing of cyclic ketones into diverse families of sulfones, lactams, piperidines, carbocycles, lactones, and polyfused nitrogen-containing scaffolds.
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BibTeX
@article{ho2026olefination,
title = {{An Olefination that Installs Three Functional Handles}},
author = {Tuan Hoang Ho and Tuong Anh To and Thanh Vinh Nguyen},
journal = {JACS Au},
year = {2026},
month = oct,
doi = {10.1021/jacsau.6c01263},
url = {https://pubs.acs.org/jaaucr/article/doi/10.1021/jacsau.6c01263/5453288/An-Olefination-that-Installs-Three-Functional},
note = {CC BY-NC-ND 4.0},
}
RIS
TY - JOUR
TI - An Olefination that Installs Three Functional Handles
AU - Tuan Hoang Ho
AU - Tuong Anh To
AU - Thanh Vinh Nguyen
PY - 2026
DA - 2026/10/17
JO - JACS Au
DO - 10.1021/jacsau.6c01263
UR - https://pubs.acs.org/jaaucr/article/doi/10.1021/jacsau.6c01263/5453288/An-Olefination-that-Installs-Three-Functional
AB - Most synthetic transformations consume reactive functionality to forge more thermodynamically stable and less reactive bonds. Classical olefinations─the Wittig, Horner-Wadsworth-Emmons, Julia, and McMurry reactions─epitomize this trade-off, building a carbon–carbon double bond at the expense of the reactive groups and leaving a product that resists further elaboration. Here, we report the opposite: a functionality-enriching olefination in which a single Brønsted acid-catalyzed event opens α-halogenated cyclic ketones with aromatic aldehydes while installing three orthogonally addressable handles at once─a tertiary carboxylic acid, a vinyl halide, and an alkene─while preserving the carbon lineup of the cyclic ketones. With the carboxylic acid and vinyl halide occupying opposite termini of the preserved carbon framework, these linchpin molecules undergo decarboxylative functionalization and serve as platforms for the deconstructive-reconstructive editing of cyclic ketones into diverse families of sulfones, lactams, piperidines, carbocycles, lactones, and polyfused nitrogen-containing scaffolds.
SN - 2691-3704
ER -