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Electronically Tuned Copper Porphyrins for the Selective Epoxidation of Alkenes

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Abstract

Four p-substituted meso-tetraphenyl metalloporphyrins [CuII(p-CH3-TPP)] (1), [CuII(p-OCH3-TPP)] (2), [CuII(p-Cl-TPP)] (3), and [CuII(p-Br-TPP)] (4) were prepared by reacting CuCl2.2H2O with free base porphyrins p-CH3-TPP (I), p-OCH3-TPP (II), p-Cl-TPP (III), and p-Br-TPP (IV) in DMF under nitrogen atmosphere. These copper porphyrins were applied as homogeneous catalysts for the epoxidation of a number of aliphatic and aromatic alkenes. Catalytic epoxidation of all the alkenes produces the corresponding epoxide with 100% selectivity along with a very high TOF value (up to a maximum of 9.623 × 103 h−1). The epoxidation of all the tested alkenes proceeded with more than 50% substrate conversion except for a few substrates. Theoretical calculation proposes that the central copper atom of the porphyrin ring remains accessible for the catalytic reaction. Moreover, the presence of electron-withdrawing groups or atoms in the para-position of the meso-substituted phenyl group of the metalloporphyrins enhances the catalytic performance. Hence, epoxidation of indene in the presence of 1–4, show 43%, 57%, 88% and 97% of substrate conversion, respectively, under optimized reaction conditions. Sterically hindered and electron-deficient alkenes are found to be difficult for epoxidation reaction. In contrast, aromatic and electron-rich alkenes with accessible double bonds easily undergo epoxidation. NaHCO3 acts as a promoter during the catalytic epoxidation and is essential for making the catalytic reaction short and efficient. The reactive intermediates peroxymonocarbonate (HCO4−) and peroxo-metalloporphyrins responsible for the catalytic epoxidation are generated in situ and identified by HR-MS and UV–Vis spectroscopy.

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All data generated or analyzed during this study are included in this published article [and its supplementary information files].

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Acknowledgements

C. H. thanks the Science and Engineering Research Board (SERB), Department of Science and Technology (DST), Government of India, New Delhi, for financial support (Grant No. EEQ/2021/000533 dated 02.03.2022) for the work. N. C. is thankful to IIT(ISM) Dhanbad for CRF postdoctoral fellowship. V. K. M. acknowledges the Department of Chemistry and Chemical Biology for providing the NMR facility. The authors acknowledge CRF IIT (ISM) Dhanbad for single-crystal XRD and HR-MS analysis. V. K. M. is thankful to IIT Ropar for carrying out mass analysis and IISER Bhopal for performing EPR analysis. GC and GC-MS used in this study were procured from the grant given by the Science and Engineering Research Board (SERB) (Grant No SB/FT/CS-027/2014) and the Department of Science and Technology (DST) (Grant No. SB/EMEQ-055/2014), respectively, of Government of India, New Delhi, India, to C. H.

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  1. Department of Chemistry & Chemical Biology, Indian Institute of Technology (Indian School of Mines), Dhanbad, 826004, Jharkhand, India

    Vivek Kumar Mishra, Nikita Chaudhary & Chanchal Haldar

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  1. Vivek Kumar Mishra
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Correspondence to Chanchal Haldar.

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Mishra, V.K., Chaudhary, N. & Haldar, C. Electronically Tuned Copper Porphyrins for the Selective Epoxidation of Alkenes. Top Catal 66, 435–451 (2023). https://doi.org/10.1007/s11244-022-01764-6

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