Chemo- and Regiodivergent Allyl-Propargyl Cross-Coupling Reactions for the Construction of 1,4-Enallenes and 1,5-Enynes

Authors

Huijun Qian
Gabriel N. Morais, Oberlin College
Katherine E. Colbaugh, Oberlin College
Junqi Su
Zili Chen
Zhiping Li
Shuming Chen, Oberlin College
Leiyang Lv

Abstract

Catalyst-controlled divergent transformations represent a vital strategy for the efficient production of structurally diverse molecules from the same readily available precursors. Herein, we report the palladium/phosphine-catalyst-driven chemo- and regiodivergent allyl-propargyl cross-coupling of propargyl carbonates with allyl boronates. Density functional theory (DFT) calculations reveal that the bidentate phosphine ligand plays a crucial role in determining the relative favorability of possible reductive elimination modes from the ƞ³-allyl-ƞ¹-allenyl palladium intermediate species. Specifically, MeO-BIPHEP facilitates the 1,1′-reductive elimination to form the 1,4-enallenes; in contrast, XantPhos favors the formation of 1,5-enynes through a 3,3′-reductive elimination pathway.

Repository Citation

Qian, Huijun, Gabriel N. Morais, Katherine E. Colbaugh, et al. 2025. "Chemo- and Regiodivergent Allyl-Propargyl Cross-Coupling Reactions for the Construction of 1,4-Enallenes and 1,5-Enynes." Angewandte Chemie International Edition: e202517878.

Publisher

Wiley-V C H Verlag GMBH

Publication Date

9-25-2025

Publication Title

Angewandte Chemie-International Edition

Department

Chemistry and Biochemistry

Document Type

Article

DOI

https://doi.org/10.1002/anie.202517878

Keywords

Allenes, Allylation, Enynes, Palladium catalysis, Propargyl carbonates

Language

English

Format

text