Citation: Chen Zhou, Yuxuan Shi, Leyang Zhang, Mengfu Dai, Lanzhu Tai, Qiang Dai, Liang-An Chen. Dynamic coordination drives regiodivergent dienylation of propargylic esters with phosphine oxides[J]. Chinese Chemical Letters, ;2026, 37(8): 112188. doi: 10.1016/j.cclet.2025.112188 shu

Dynamic coordination drives regiodivergent dienylation of propargylic esters with phosphine oxides

Chen Zhou ^{a, 1} ,
Yuxuan Shi ^{a, 1} ,
Leyang Zhang ^a ,
Mengfu Dai ^a ,
Lanzhu Tai ^a ,
Qiang Dai ^{a, *,} ,
Liang-An Chen ^{a, b, *,}

a.
State Key Laboratory of Microbial Technology, Jiangsu Collaborative Innovation Center of Biomedical Functional Materials, School of Chemistry and Materials Science, Nanjing Normal University, Nanjing 210023, China
b.
State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, China

daiq@njnu.edu.cn

lachen@njnu.edu.cn

Received Date: 1 September 2025
Revised Date: 13 November 2025
Accepted Date: 26 November 2025
Available Online: 27 November 2025

Figures(6)

Transition-metal-catalyzed substitution of propargylic electrophiles with secondary phosphine oxides (SPOs) has emerged as a powerful strategy to phosphorus-containing frameworks. However, precise regiocontrol remains elusive due to competing pathways in allenyl-metal intermediates and SPO tautomerism. Herein, we report a dynamic coordination strategy that leverages the tunable binding modes of SPOs to achieve regiodivergent dienylation of propargylic esters, thereby accessing a diverse range of 1,3-dienyl phosphines. Through fine-tuning of ligands and the strategic use of Brønsted or Lewis acid-assisted catalytic systems, we demonstrate switchable C2- versus C3-selective dienylation, governed by dynamic control over the coordination modes and reactivities of SPOs. Mechanistic studies reveal that the dynamic inner- or outer-sphere coordination dictates the regiochemical outcome, which proceeds via relay catalysis or bimetallic cooperative catalysis pathways, thus offering a rationale for the observed regiodivergence. This method provides a robust and modular platform for synthesizing multisubstituted 1,3-dienyl phosphines with broad substrate scope and excellent regio- and stereoselectivity, underscoring the potential of coordination-controlled reactivity in complex bond-forming processes.
- Regiodivergent,
- Dienylation,
- Propargylic esters,
- Phosphine oxides,
- Dynamic coordination
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