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Monday, October 25, 2021
Douglass F. Taber
University of Delaware

Reactions of Alkenes: The Park Synthesis of Nitramine

Gong-Qing Liu and Yong Ling of Nantong University prepared the selenyl alcohol 2 by the oxidative addition of diphenyl diselenide to the alkene 1 (J. Org. Chem. 2021, 86, 5292. DOI: 10.1021/acs.joc.1c00257). Bill Morandi of ETH Zürich effected the selective azido amination of the alkene 3, leading to 4 (J. Am. Chem. Soc. 2020, 142, 21548. DOI: 10.1021/jacs.0c11025). Wanmei Liu and Pengfei Zhang of Hangzhou Normal University and Qing Zhu of the Zhejiang University of Technology combined the alkene 5 with TMS azide and an aryl diazonium salt to give the dialkyl diazene 6 (Org. Lett. 2021, 23, 1204. DOI: 10.1021/acs.orglett.0c04148). Takuya Hashimoto of Chiba University assembled the cyclic urethane 10 by the addition of the sulfonamide 8 to the alkene 7 (J. Am. Chem. Soc. 2021, 143, 1745. DOI: 10.1021/jacs.0c11440). Frank Glorius of the Westfälische Wilhelms-Universität Münster described a parallel investigation (Nature Catal. 2021, 4, 54. DOI: 10.1038/s41929-020-00553-2).

Gui-Juan Cheng of the Chinese University of Hong Kong and Xianjie Fang of Shanghai Jiao Tong University developed a Ni catalyst for the selective terminal migratory hydrocyanation of an internal alkene 11 with acetone cyanohydrin 12, leading to the cyano ester 13 (Org. Lett. 2021, 23, 486, DOI: 10.1021/acs.orglett.0c04007; Angew. Chem. Int. Ed. 2021, 60, 1883, DOI: 10.1002/anie.202011231). Joyram Guin of the Indian Association for the Cultivation of Science devised the assembly of the ketone 16 by the visible light-promoted coupling of the alkene 14 with the aldehyde 15 (Chem. Eur. J. 2021, 27, 4412. DOI: 10.1002/chem.202004946). Zheng-Hui Guan of Northwest University developed the Pd-catalysed Markovnikov carbonylative coupling of the alkene 17 with aniline 18, leading to the amide 19 (J. Am. Chem. Soc. 2021, 143, 7298. DOI: 10.1021/jacs.1c03454). Xi-Sheng Wang of the University of Science and Technology of China used a Cu catalyst to mediate the assembly of the chloro azide 22 by the combination of the alkene 20, bromochloromethane 21 and trimethylsilyl azide (Chem. Commun. 2021, 57, 5666. DOI: 10.1039/D1CC01751A). Antonio M. Echavarren of ICIQ coupled the alkene 23 with the bromoalkyne 24 to give the enyne 25 (Angew. Chem. Int. Ed. 2021, 60, 5693. DOI: 10.1002/anie.202014877). Professor Glorius reported related results (Angew. Chem. Int. Ed. 2021, 60, 5688. DOI: 10.1002/anie.202015249). M. Kevin Brown of Indiana University assembled the β-silyl ketone 28 by the addition of ClZnSiMe2Ph and benzoyl chloride 27 to the alkene 26 (ACS Catal. 2021, 11, 1858. DOI: 10.1021/acscatal.0c05449).

Hajime Ito of Hokkaido University prepared the boronate 31 by the Cu-catalyzed addition of the tertiary bromide 30 to the alkene 29 (J. Am. Chem. Soc. 2021, 143, 5260. DOI: 10.1021/jacs.1c02050). Professor Brown, Professor Glorius and Kendall N. Houk of UCLA uncovered the photochemically-promoted construction of the tricyclic pyridine 34 by the cycloaddition of the quinoline 33 to the alkene 32 (Science 2021, 371, 1338. DOI: 10.1126/science.abg0720).

Many of the Nitraria alkaloids, exemplified by nitramine 38, contain the 2-azaspiro[5,5]undecane ring structure. In the course of a synthesis of 38, Hyeung-geung Park of Seoul National University coupled the readily-prepared alkene 35 with the Zard reagent 36, leading to 37 (J. Org. Chem. 2021, 86, 4375. DOI: 10.1021/acs.joc.0c02573).

D. F. Taber, Org. Chem. Highlights 2021, October 25.