Citation: Jun Gu, Wan-Yi Xu, Rong-Gui Zhou, Zhiwen Ye, Ying He. Divergent β-hydride elimination in Pd-catalyzed intra- and intermolecular Heck reactions toward axially chiral alkene frameworks[J]. Chinese Chemical Letters, ;2026, 37(11): 112506. doi: 10.1016/j.cclet.2026.112506 shu

Divergent β-hydride elimination in Pd-catalyzed intra- and intermolecular Heck reactions toward axially chiral alkene frameworks

Jun Gu ^{a, 1} ,
Wan-Yi Xu ^{a, 1} ,
Rong-Gui Zhou ^a ,
Zhiwen Ye ^a ,
Ying He ^{a, b, c, *,}

a.
School of Chemistry and Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, China
b.
Jiangsu Key Laboratory of Advanced Structural Materials and Application Technology, Nanjing Institute of Technology, Nanjing 211167, China
c.
Key Laboratory of Molecule Synthesis and Function Discovery, Fujian Province University, College of Chemistry at Fuzhou University, Fuzhou 350108, China

yhe@njust.edu.cn

Received Date: 3 January 2026
Revised Date: 31 January 2026
Accepted Date: 5 February 2026
Available Online: 7 February 2026

Figures(9)

This work herein demonstrates the first palladium-catalyzed chirality transfer from enantioenriched allylic substrates to efficiently and selectively construct both indenes and acyclic alkene atropisomers through tunable intra- and intermolecular Heck reactions. Experimental and computational studies reveal a mechanistic divergence between intramolecular and intermolecular Heck reactions, as evidenced by their distinct β-hydride elimination orientations. The intramolecular pathway is favored by the thermodynamic stability provided by conjugation and the alleviation of steric strain through ring formation, enabling direct atroposelective cyclization. In contrast, the intermolecular pathway lacks the substantial energetic benefit of ring closure, while introducing significant steric encumbrance, thereby leading to divergent pathways in the β-hydride elimination step. Despite this, subsequent olefin positional and Z/E geometric isomerization following the Heck reaction can also effectively construct acyclic axially chiral alkene frameworks. The reaction demonstrates broad substrate scope with consistently high enantioselectivity for both product classes.
- Pd catalysis,
- Divergent β-hydride elimination,
- Axial chirality,
- Indenes,
- Acyclic alkenes
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