Citation: Jun Yan, Shenghao Jiang, Yin Wei, Min Shi. Palladium-catalyzed and ligand-controlled regiodivergent intramolecular cyclization of ketone-vinylbicyclo[1.1.0]butanes (Ketone-VC-BCBs)[J]. Chinese Chemical Letters, ;2026, 37(11): 112369. doi: 10.1016/j.cclet.2026.112369 shu

Palladium-catalyzed and ligand-controlled regiodivergent intramolecular cyclization of ketone-vinylbicyclo[1.1.0]butanes (Ketone-VC-BCBs)

Jun Yan ^a ,
Shenghao Jiang ^a ,
Yin Wei ^{b, *,} ,
Min Shi ^{a, b, *,}

a.
Key Laboratory for Advanced Materials and Institute of Fine Chemicals, Key Laboratory for Advanced Materials and Feringa Nobel Prize Scientist Joint Research Center, School of Chemistry & Molecular Engineering, East China University of Science and Technology, Shanghai 200237, China
b.
State Key Laboratory of Organometallic Chemistry, Center for Excellence in Molecular Synthesis, University of Chinese Academy of Sciences, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China

weiyin@sioc.ac.cn

mshi@mail.sioc.ac.cn

Received Date: 29 October 2025
Revised Date: 26 December 2025
Accepted Date: 5 January 2026
Available Online: 5 January 2026

Figures(6)

A palladium-catalyzed and ligand-controlled regiodivergent intramolecular cyclization of ketone–vinylbicyclo[1.1.0]butanes (Ketone-VC-BCBs) has been developed. Using Trost-Ph-Phos as the ligand, intramolecular nucleophilic attack of the carbonyl group onto the zwitterionic palladium species followed by a proton transfer affords oxaspiro[3.4]oct-1-en-5-one derivatives in moderate yields with excellent diastereoselectivities. In contrast, employment of 1,4-bis(diphenylphosphino)butane (DPPB, L3) promotes intramolecular a proton migration and a rearrangement to generate a novel zwitterionic palladium species, which subsequently undergoes cyclization to deliver unexpected rearranged products as bicyclo[3.1.1]heptanes in good yields. Ligand-controlled modulation of proton transfer pathways governs the divergent reaction outcomes, enabling the selective formation of two structurally distinct products. The proposed mechanisms were further supported by deuterium-labeling experiments and DFT calculations. The further transformation of the obtained products has also been presented.
- Palladium catalysis,
- Divergent synthesis,
- Zwitterionic palladium species,
- Ketone-VC-BCBs
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