Organic Chemistry Portal
Organic Chemistry Highlights

Monday, May 25, 2020
Douglass F. Taber
University of Delaware

Reactions of Alkenes: The Breit Synthesis of Vermiculine

Dengfu Lu and Yuefa Gong of the Huazhong University of Science and Technology prepared 2 by the double functionalization of the alkene 1 (Adv. Synth. Catal. 2019, 361, 5565. DOI: 10.1002/adsc.201901041). Zhen Fang and Kai Guo of Nanjing Technical University oxidized the alkene 3 to the α-keto thioester 4 (Eur. J. Org. Chem. 2019, 4056. DOI: 10.1002/ejoc.201900585). Rodney A. Fernandes of the Indian Institute of Technology Bombay effected the selective Wacker oxidation of 5 to the aldehyde 6 (Org. Lett. 2019, 21, 5827. DOI: 10.1021/acs.orglett.9b01897). John F. Hartwig of the University of California, Berkeley developed a protocol for the net contra-thermodynamic isomerization of the alkene 7 to the alkene 8 (Org. Lett. 2019, 21, 7129. DOI: 10.1021/acs.orglett.9b02695).

Robert Franke of Evonik and Matthias Beller of the Leibniz-Institut für Katalyse e .V. an der Universität Rostock effected the migratory carboxylation of the alkene 9 to the acid 10 (Angew. Chem. Int. Ed. 2019, 58, 14365. DOI: 10.1002/anie.201908451). Armido Studer of the Westfalisches Wilhelms-Universität developed a radical amination/trapping, assembling 14 by combining 11 with 12 and 13 (Angew. Chem. Int. Ed. 2019, 58, 16528. DOI: 10.1002/anie.201910926). Yian Shi of Colorado State University observed that the Heck-like addition of the Grignard reagent 16 to the alkene 15 in the presence of 17 delivered 18 with remarkable regioselectivity (Org. Lett. 2019, 21, 5157. DOI: 10.1021/acs.orglett.9b01762). Ruben Martin of ICIQ showed that the Katritzky salt 19 could be added to 20, leading to 21 (J. Am. Chem. Soc. 2019, 141, 16197. DOI: 10.1021/jacs.9b07489).

Ming-Yu Ngai of Stony Brook University devised the addition of 23 to 22 to give the diketone 24 (ACS Catal. 2019, 9, 10358. DOI: 10.1021/acscatal.9b03570). Jonathan A. Ellman of Yale University assembled 28 by adding 26 and 27 to 25 (Nature Catal. 2019, 2, 756. DOI: 10.1038/s41929-019-0330-7). Guoyin Yin of Wuhan University developed the 1,1-doubly branching functionalization of 11 to 29 (Angew. Chem. Int. Ed. 2019, 58, 8872. DOI: 10.1002/anie.201903890). Zhiwei Zuo of ShanghaiTech University described the fragmentative addition to 31 of the primary alcohol derived from 30, leading to 32 (J. Am. Chem. Soc. 2019, 141, 10556. DOI: 10.1021/jacs.9b05932).

High regioselectivity can sometimes be achieved in the Wacker oxidation of internal olefins. This is illustrated by the conversion of 33 to vermiculine 34 reported by Bernhard Breit of the Albert-Ludwigs-Universität Freiburg (Chem. Eur. J. 2019, 25, 3532. DOI: 10.1002/chem.201900216).

D. F. Taber, Org. Chem. Highlights 2020, May 25.