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Organic Chemistry Highlights

Monday, January 27, 2025
Douglass F. Taber
University of Delaware

Reactions of Alkenes: The Ho Synthesis of Isocyanoallopupukeanane

Azim Ziyaei Halimehjani of the Sharif Institute of Technology and Bilal Nisanci of Atatürk University devised the Markonikov hydrothiolation of the alkene 1 with pyrrolidine 2 and carbon disulfide, leading to the dithiocarbamate 3 (J. Org. Chem. 2024, 89, 5353. DOI: 10.1021/acs.joc.3c02722). Jian-Ji Zhong of Shantou University described a parallel investigation (Org. Chem. Front. 2024, 11, 646. DOI: 10.1039/D3QO01632C). Xinxin Wu and Xiaoguang Bao of Soochow University reported the anti-Markovnikov amination of the alkene 4 to the sulfonamide 5 (Angew. Chem. Int. Ed. 2024, 63, e202406069. DOI: 10.1002/anie.202406069). Guosheng Liu of the Shanghai Institute of Organic Chemistry reported a related result, the alkene-migrating conversion of 6 to the terminal sulfonamide 8 (J. Am. Chem. Soc. 2024, 146, 13536. DOI: 10.1021/jacs.4c03283). Manoj V. Mane and Shubhankar Kumar Bose of Jain University effected the borylation of the alkene 9, leading to the alkenyl boronate 10 (ACS Catal. 2024, 14, 3065. DOI: 10.1021/acscatal.3c05742).

In a process complementary to Simmons-Smith cyclopropanation, Philippe Renaud of the University of Bern and Christoforos G. Kokotos of the National and Kapodistrian University of Athens added the iodomethylboronate 12 to the alkene 11, leading to the cyclopropane 13 (Chem. Eur J. 2024, 30, e202400253. DOI: 10.1002/chem.202400253). David W. C. MacMillan of Princeton University constructed the quaternary center of 16 by the addition of the alcohol 15 to the alkene 14 (J. Am. Chem. Soc. 2024, 146, 12300. DOI: 10.1021/jacs.4c02316). Hai-Chao Xu of Xiamen University developed the electrochemical oxidation of the alkene 17 to the azido nitrile 18 (Angew. Chem. Int. Ed. 2024, 63, e202313273. DOI: 10.1002/anie.202313273). Nuno Maulide of the University of Vienna used a charge relocation strategy to effect the diastereoselective preparation of the 3-acyl cyclohexanol 21 by the combination of the cyclohexene 19 with benzoyl chloride 20 (Nature 2024, 626, 92. DOI: 10.1038/s41586-023-06938-0).

Raphael Wischert of Syensqo and François Jérôme of the University of Poitiers established the double homologation of the alkene 22, leading to the α-methylene aldehyde 23 (Chem. Eur. J. 2024, 30, e202400601. DOI: 10.1002/chem.202400601). Yibiao Li of Wuyi University and Huanfeng Jiang of the South China University of Technology assembled the ester 26 by the Pd-catalyzed coupling of the alkene 24 with the bromoalkyne 25 (Org. Chem. Front. 2024, 11, 3451. DOI: 10.1039/D4QO00504J). Zhankui Sun of Shanghai Jiao Tong University constructed the ketone 30 by adding the α-sulfinyl ester 28 to the alkene 27, then adding the enol ether 29 (Org. Lett. 2024, 26, 2585. DOI: 10.1021/acs.orglett.4c00611). In an extension of the work cited above, Professor MacMillan prepared the ester 33 by the addition of the alcohol 31 and α-chloromalonate 32 to the alkene 14 (Nature 2024, 628, 104. DOI: 10.1038/s41586-024-07165-x).

2-Isocyanoallopupukeanane (36) was isolated from the nudibranch Phyllidiella putulosa. Tse-Lok Ho of the National Chiao Tung University reported in 2000 that a Ritter reaction converted the alkene 34 into the formamide 35, that could be dehydrated to 36 (J. Org. Chem. 2000, 65, 5774. DOI: 10.1021/jo000668w). For a more recent alternative, see Reactions of Alkenes: The Tanino Synthesis of 2-Isocyanoallopupukeanane 2023, May 22.

D. F. Taber, Org. Chem. Highlights 2025, January 27.
URL: https://www.organic-chemistry.org/Highlights/2025/27January.shtm