Organic Chemistry Portal
Organic Chemistry Highlights

Monday, February 18, 2019
Douglass F. Taber
University of Delaware

Alkylated Stereogenic Centers: The Hoveyda Synthesis of Heliespirone C

Jianwei Sun of the Hong Kong University of Science and Technology opened the prochiral azetidine 1 with 2 to give 3 in high ee (Angew. Chem. Int. Ed. 2018, 57, 3763. DOI: 10.1002/anie.201712395). Stephen L. Buchwald of MIT effected the double reduction of 4 to the aldehyde 5 (J. Am. Chem. Soc. 2018, 140, 606. DOI: 10.1021/jacs.7b12260). Jiean Chen and Yong Huang of the Shenzhen Graduate School of Peking University prepared the thioester 8 by coupling the aldehyde 6 with the thiol 7 (Chem. Commun. 2018, 54, 1473. DOI: 10.1039/C7CC09549J). Hui Lv of Wuhan University and Xumu Zhang of the Southern University of Science and Technology hydrogenated 9 to 10 (Chem. Sci. 2018, 9, 1919. DOI: 10.1039/C7SC04639A). Professor Zhang and Qin Yin, also of the Southern University of Science and Technology, reported the hydrogenation of 11 to the pyrrolidinone 12 (ACS Catal. 2018, 8, 4824. DOI: 10.1021/acscatal.8b00827).

Jared C. Lewis of the University of Chicago designed variations on rebeccamycin halogenase (RebH) that effected enantioselective chlorination of 13 to 14. The absolute configuration of the product 14 had not yet been assigned (J. Am. Chem. Soc. 2018, 140, 546. DOI: 10.1021/jacs.7b09573).

Erick M. Carreira of the Eidgenössische Technische Hoschule Zürich coupled 15 with 16 to give the acetal 17 (Angew. Chem. Int. Ed. 2018, 57, 7654. DOI: 10.1002/anie.201803558). Steven J. Malcomson of Duke University assembled 20 by adding 19 to the diene 18 (J. Am. Chem. Soc. 2018, 140, 2761. DOI: 10.1021/jacs.7b13300). Xin Hong of Zhejiang University and Shi-Liang Shi of the Shanghai Institute of Organic Chemistry established a strategy for the overall coupling of 21 with vinylmagnesium bromide, leading to 22 (Angew. Chem. Int. Ed. 2018, 57, 1376. DOI: 10.1002/anie.201711229). Taichi Kano and Keiji Maruoka of Kyoto University combined 23 with 24 to give, after diastereoselective reduction and elimination, the Z alkene 25 (Chem. Commun. 2018, 54, 176. DOI: 10.1039/C7CC08691A).

Tsuyoshi Miura of the Tokyo University of Pharmacy and Life Sciences achieved high ee in the addition of 26 to 27 to give 28 (J. Org. Chem. 2018, 83, 2402. DOI: 10.1021/acs.joc.7b02976). Ilan Marek of Technion-Israel Institute of Technology isomerized the cyclopropylcarbinol 29 to the aldehyde 30 (Adv. Synth. Catal. 2018, 360, 1389. DOI: 10.1002/adsc.201701481).

Amir H. Hoveyda of Boston College combined 31 with 32 to give the borate ester 33, thus establishing the absolute configuration of heliespirone C (34) (Nature Chem. 2018, 10, 99. DOI: 10.1038/nchem.2861). Jaesook Yun of Sungkyunkwan University described related results (Org. Lett. 2017, 19, 6144. DOI: 10.1021/acs.orglett.7b03022).

D. F. Taber, Org. Chem. Highlights 2019, February 18.