Organic Chemistry Portal
Organic Chemistry Highlights

Monday, June 12, 2023
Douglass F. Taber
University of Delaware

Benzene Derivatives: The Dudley Synthesis of Coprinol

Hongjian Lu of Nanjing University used an Ir catalyst to mediate the regioselective ortho amination of the benzamide 1, leading to the protected anthranilamide 2 (J. Org. Chem. 2022, 87, 13990. DOI: 10.1021/acs.joc.2c01636). Jin-Quan Yu of Scripps/La Jolla employed a Pd catalyst to direct the ortho hydroxylation of the arylacetic acid 3 to give the phenol 4 (J. Am. Chem. Soc. 2022, 144, 18109. DOI: 10.1021/jacs.2c08332).

Wenbo H. Liu of Sun Yat-sen University oxidized the benzoic acid 5 to the phenol 6 (J. Am. Chem. Soc. 2022, 144, 15894. DOI: 10.1021/jacs.2c07529). Zhibo Liu of Peking University converted the benzoic acid 7 into the aryl boronate 8 (Nature Commun. 2022, 13, 7112. DOI: 10.1038/s41467-022-34833-1).

Chengrong Ding of the Zhejiang University of Technology activated the phenol 9 with SO2F2, then used a Pd catalyst to couple the intermediate with trimethylboroxine (10), leading to the methyl arene 11 (Org. Biomol. Chem. 2022, 20, 7640. DOI: 10.1039/D2OB01523D). Tobias Ritter of the Max-Planck-Institut für Kohlenforschung further demonstrated the versatility of aryl thianthrenium salts, activating the arene 12 with 13, then coupling the intermediate with methyl acrylate 14 to give the α-bromo ester 15 (Angew. Chem. Int. Ed. 2022, 61, e202209882. DOI: 10.1002/anie.202209882).

Igor Larrosa of the University of Manchester assembled the arene 18 by effecting the regioselective ortho methylation of the benzylic alcohol 16, using the ammonium salt 17 as the methyl donor (JACS Au 2022, 2, 2529. DOI: 10.1021/jacsau.2c00399). Augustí Lledós of the Universitat Autňnoma de Barcelona and Ana C. Albéniz of the Universidad de Valladolid prepared the biphenyl 20 by the ortho arylation of the aniline 19 (ACS Catal. 2022, 12, 14527. DOI: 10.1021/acscatal.2c05206). Jan Otevrel and Pavel Bobal of Masaryk University Brno used a Cinchona derived catalyst to mediate the enantioselective assembly of the benzylic alcohol 23 by the coupling of the benzaldehyde 21 with chloral 22 (Adv. Synth. Catal. 2022, 364, 2174. DOI: 10.1002/adsc.202200180). Lu Liu of East China Normal University employed a BINOL-derived phosphoric acid to direct the Au/Ag-catalyzed coupling of the α-diazo ester 25 with the arene 24, leading to the aryl acetate 26 in high ee and with high regioselectivity (Angew. Chem. Int. Ed. 2022, 61, e202208874. DOI: 10.1002/anie.202208874).

Janakiram Vaitla of the Indian Institute of Technology Delhi combined the sulfonium ylide 27 with ethyl acrylate 28 to give the benzoate 29 (Org. Lett. 2022, 24, 8359. DOI: 10.1021/acs.orglett.2c03388). Zhi-Shi Ye of the Dalian University of Technology used a phosphine catalyst to prepare the trisubstituted benzene 32 by the coupling of the cyclopropyl acetylene 30 with the alkyne 31 (Org. Lett. 2022, 24, 6489. DOI: 10.1021/acs.orglett.2c02201).

Coprinol (36) is an illudalane sesquiterpene isolated from the edible mushroom Coprinopsis cinerea. Gregory B. Dudley of the West Virginia University assembled the bicyclic core 35 of 36 by the Rh-catalyzed aromatizing combination of the alkyne 34 with the diyne 33 (J. Org. Chem. 2022, 87, 14909. DOI: 10.1021/acs.joc.2c01741).

D. F. Taber, Org. Chem. Highlights 2023, June 12.