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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. ). Bill Morandi of ETH Zürich effected the selective azido amination of the alkene 3, leading to 4 (J. Am. Chem. Soc. 2020, 142, 21548. ). 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. ). 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. ). Frank Glorius of the Westfälische Wilhelms-Universität Münster described a parallel investigation (Nature Catal. 2021, 4, 54. ).

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, ; Angew. Chem. Int. Ed. 2021, 60, 1883, ). 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. ). 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. ). 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. ). 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. ). Professor Glorius reported related results (Angew. Chem. Int. Ed. 2021, 60, 5688. ). 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. ).

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. ). 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. ).

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. ).

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