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Organic Chemistry Highlights

Monday, March 25, 2024
Douglass F. Taber
University of Delaware

Reactions of Alkenes: The Wood Synthesis of Alterbrassicicene C

Tobias Ritter of Max Planck Institute für Kohlenforschung showed that the nitrate ester 2 prepared from the alkene 1 could readily be converted to the corresponding iodide or alcohol (Nature Catal. 2023, 6, 196. DOI: 10.1038/s41929-023-00914-7). Gary A. Molander of the University of Pennsylvania prepared the sulfone 5 by adding the sulfonyl fluoride 4 to the alkene 3 (Org. Lett. 2023, 25, 2084. DOI: 10.1021/acs.orglett.3c00447). Alexandre Pradal and Giovanni Poli of Sorbonne Université found that the benzenesulfinate 7 could be added to the alkene 6 to give the allylic sulfone 8 (Eur. J. Org. Chem. 2023, 26, e202201493. DOI: 10.1002/ejoc.202201493). Kangjiang Liang and Chengfeng Xia of Yunnan University devised an alternative protocol that led to the corresponding alkenyl sulfone, not illustrated (Chem. Commun. 2023, 59, 462. DOI: 10.1039/D2CC06101E).

Frank Glorius of the Westfälische Wilhelms-Universität Münster assembled the sultam 11 by adding the reagent 10 to the alkene 9 (J. Am. Chem. Soc. 2023, 145, 2364. DOI: 10.1021/jacs.2c11295). Zhankui Sun of the Shanghai Jiao Tong University used 5,5'-dimethyl-2,2'-bipyridine to mediate the conversion of the alkene 1 to the thioester 12 (Org. Lett. 2023, 25, 4173. DOI: 10.1021/acs.orglett.3c01481). Szilárd Varga and Tibor Soós of the Institute of Organic Chemistry, Budapest effected Kornblum oxidation of the thianthrenium salt derived from 9, leading to the Z-unsaturated aldehyde 13 (Angew. Chem. Int. Ed. 2023, 62, e202214096. DOI: 10.1002/anie.202214096).

Julia Rehbein and Oliver Reiser of the Universität Regensburg used a Cu photocatalyst to promote the addition of bromonitromethane 14 to the alkene 1, leading to the γ-bromo nitroalkane 15 (Angew. Chem. Int. Ed. 2023, 62, e202219086. DOI: 10.1002/anie.202219086). Kensuke Kiyokawa and Satoshi Minakata of Osaka University employed the sulfonyl cyanide 16 to convert the alkene 1 to the β-hydroxy nitrile 17 (Angew. Chem. Int. Ed. 2023, 62, e202218743. DOI: 10.1002/anie.202218743).

Professor Sun and Wei Deng, also of the Shanghai Jiao Tong University, achieved specific deuteration in the course of the addition of the mercapto ester 18 to the alkene 1, leading to the ester 19 (Tetrahedron Lett. 2022, 101, 153914. DOI: 10.1016/j.tetlet.2022.153914). Fan Yang and Yangjie Wu of Zhengzhou University constructed the β-lactone 22 by adding the bromoester 21 to the alkene 20 (Org. Chem. Front. 2023, 10, 2517. DOI: 10.1039/D3QO00096F). In a parallel development, Tomislav Rovis of Columbia University used α-Br-imides to assemble γ-lactams (Chem. Sci. 2023, 14, 1569. DOI: 10.1039/D2SC05973H). Hegui Gong of Shanghai University effected the hydrodimerization of the alkene 23, leading to 24 (Nature Synthesis 2023, 2, 364. DOI: 10.1038/s44160-023-00239-0). Tehshik P. Yoon of the University of Wisconsin added the elements of the β-keto ester 26 across the alkene 25 to give the δ-keto ester 27 (Org. Lett. 2023, 25, 4098. DOI: 10.1021/acs.orglett.3c01321).

Alterbrassicicene C (30) was isolated from the fungal plant pathogen Alternaria brassicicola. In the early stages of a synthesis of 30, John L. Wood of Baylor University used the Grubbs catalyst to migrate the alkene of 28, then ozonized the resulting internal alkene, leading to the aldehyde 29 (J. Am. Chem. Soc. 2023, 145, 37. DOI: 10.1021/jacs.2c12275).

D. F. Taber, Org. Chem. Highlights 2024, March 25.
URL: https://www.organic-chemistry.org/Highlights/2024/25March.shtm