C-H Functionalization: The Li/She Synthesis of Pepluacetal

Peng Hu of Sun Yat-sen University selectively converted the alkane 1 into the terminal boronate 2 (Science 2024, 383, 537. DOI: 10.1126/science.adj9258). John F. Hartwig of the University of California, Berkeley reported related results (J. Am. Chem. Soc. 2024, 146, 7124. DOI: 10.1021/jacs.3c12981). Xiaohua Liu and Xiaoming Feng of Sichuan University effected the oxidative coupling of the acyl imidazole 3 with the alkene 4, leading to 5 in high ee (Angew. Chem. Int. Ed. 2024, 63, e202314256. DOI: 10.1002/anie.202314256). Ming Yan, also of Sun Yat-sen University, used a Pd catalyst to mediate the coupling of the diazomalonate 7 with the amide 6 to give the diester 8 (Org. Lett. 2024, 26, 2523. DOI: 10.1021/acs.orglett.4c00038). Richmond Sarpong, also of the University of California, Berkeley assembled the ketone 11 by the distal functionalization of the camphor derivative 9 with methyl vinyl ketone 10 (J. Am. Chem. Soc. 2024, 146, 7850. DOI: 10.1021/jacs.4c01351).

Guillaume Prestat and Farouk Berhal of Université Paris Cité used an iron catalyst to cyclize the N-acetoxy amide 12 to the lactone 13 (ACS Catal. 2024, 14, 4329. DOI: 10.1021/acscatal.3c04900). Kazunori Nagao and Hirohisa Ohmiya of Kyoto University used the pyridinium salt 15 in conjunction with a Co catalyst to cyclize the vinyl sulfonamide 14 to the azetidine 16 (ACS Catal. 2024, 14, 8005. DOI: 10.1021/acscatal.4c02004). Junbiao Chang and Wenquan Yu of Zhengzhou University effected the oxidative cyclization of the sufonamide 17 to the pyrrolidine 18 (J. Org. Chem. 2024, 89, 3481. DOI: 10.1021/acs.joc.3c02901). Feng-Lian Zhang, Yao Fu and Yi-Feng Wang of the University of Science and Technology of China demonstrated that the boryl radical 20 cyclized the amine 19 to the pyrrolidine 21 (Science 2023, 382, 1056. DOI: 10.1126/science.adg1322).

Marcos G. Suero of ICIQ achieved high diastereoselectivity in the Rh-mediated cyclization of the diazo ester 22 to the tetrahydrofuran 23 (J. Am. Chem. Soc. 2024, 146, 12294. DOI: 10.1021/jacs.4c00867). Earlier, we reported the cyclization of the diazo ester 24 to the tetrahydrofuran 25 (J. Org. Chem. 1996, 61, 6706. DOI: 10.1021/jo960758u).

Jin-Quan Yu of Scripps/La Jolla observed both high diastereoselectivity and enantioselectivity in the preparation of the cyclopentanecarboxylic acid 28 by the coupling of the prochiral acid 26 with the aryl iodide 28 (Science 2024, 384, 793. DOI: 10.1126/science.ado1246). Nuno Maulide of the University of Vienna achieved the transannular cyclization of the cyclodecane 29 to the trans decalin 30 (Science 2024, 384, 815. DOI: 10.1126/science.adi8).

Pepluacetal (33) was isolated from the petty spurge Euphorbia peplus, long used to treat skin lesions. Huilin Li and Xuegong She of Lanzhou University first assembled the cyclobutane 31, then functionalized it by Rh-mediated intramolecular C-H insertion, leading to 32 (Angew. Chem. Int. Ed. 2024, 63, e202400943. DOI: 10.1002/anie.202400943).