Controlled oligomerization of [1.1.1]propellane through radical polarity matching: selective synthesis of SF5- and CF3SF4-containing [2]staffanes

Jón Atiba Buldt; Wang-Yeuk Kong; Yannick Kraemer; Masiel M Belsuzarri; Ansh Hiten Patel; James C Fettinger; Dean J Tantillo; Cody Ross Pitts

doi:10.3762/bjoc.20.259

Controlled oligomerization of [1.1.1]propellane through radical polarity matching: selective synthesis of SF₅- and CF₃SF₄-containing [2]staffanes

Beilstein J Org Chem. 2024 Nov 29:20:3134-3143. doi: 10.3762/bjoc.20.259. eCollection 2024.

Authors

Jón Atiba Buldt^#¹, Wang-Yeuk Kong^#¹, Yannick Kraemer¹, Masiel M Belsuzarri¹, Ansh Hiten Patel¹, James C Fettinger¹, Dean J Tantillo¹, Cody Ross Pitts¹

Affiliation

¹ Department of Chemistry, University of California, Davis, 1 Shields Avenue, Davis, CA 95616, U.S.A.

^# Contributed equally.

Abstract

Selectivity in radical chain oligomerizations involving [1.1.1]propellane - i.e., to make [n]staffanes - has been notoriously challenging to control when n > 1 is desired. Herein, we report selective syntheses of SF₅- and CF₃SF₄-containing [2]staffanes from SF₅Cl and CF₃SF₄Cl, demonstrating cases whereby oligomerization is preferentially truncated after incorporation of two bicyclopentane (BCP) units. Synthetic and computational studies suggest this phenomenon can be attributed to alternating radical polarity matching. In addition, single-crystal X-ray diffraction (SC-XRD) data reveal structurally interesting features of the CF₃SF₄-containing [2]staffane in the solid state.

Keywords: [1.1.1]propellane; pentafluorosulfanylation; radical chain oligomerization; staffanes; strain-release.

Grants and funding

C.R.P. thanks the NIH/NIGMS (R35GM150861) and the University of California, Davis for financial support. W.Y.K thanks the Croucher Foundation for financial support through a doctoral scholarship. W.Y.K. and D.J.T. thank the NSF ACCESS program (CHE030089) for computational support. The authors also thank the NSF (CHE1531193) for the Dual Source X-ray Diffractometer.