Organic Chemistry Portal
Organic Chemistry Highlights

Monday, June 10, 2024
Douglass F. Taber
University of Delaware

Benzene Derivatives: The Guo Synthesis of Fumimycin

Daniel H. Ess of BYU and László Kürti of Rice University reported the amination of the nitro anisole 1 with the hydroxylamine derivative 2, leading to the aniline 3 (J. Org. Chem. 2023, 88, 11847. DOI: 10.1021/acs.joc.3c01127). Yueyue Ma and Jinxing Ye of the East China University of Science and Technology and the Guangdong University of Technology described a complementary protocol for arene amination (Eur. J. Org. Chem. 2023, 26, e202300553. DOI: 10.1002/ejoc.202300553). Kyungsoo Oh of Chung-Ang University showed that the areneazo-2-(2-nitropropane) 4, readily prepared by diazotization of the corresponding aniline, could be coupled with an alcohol 5, leading to the ether 6 (Org. Lett. 2023, 25, 7204. DOI: 10.1021/acs.orglett.3c02783).

Tobias Ritter of the Max-Planck Institut für Kohlenforschung coupled the aniline 7 with the sulfoxide 8 to give the intermediate arylthiarenium salt, that was then combined with acrylonitrile 9 in the presence of sodium azide, leading to the α-azido nitrile 10 (J. Am. Chem. Soc. 2023, 145, 13542. DOI: 10.1021/jacs.3c04016). David R. Stuart of Portland State University showed that the arylthiarenium salt 11 could be eliminated under mild conditions and with high regioselectivity to give the aryne, that coupled with the nitrone 12 to give 13 (J. Am. Chem. Soc. 2023, 145, 3306. DOI: 10.1021/jacs.2c13007). Haohua Huo of Xiamen University achieved high enantioselectivity in the preparation of the secondary benzamide 16 by the decarboxylative coupling of the N-hydroxyphthalimide ester 15 with the bromoarene 14 (Angew. Chem. Int. Ed. 2023, 63, e202305889. DOI: 10.1002/anie.202305889). Dawei Ma of the Shanghai Institute of Organic Chemistry also achieved high enantioselectivity in the coupling of the cyanoacetate 18 with the iodoanisole 17, leading to the α-cyanoester 19 (Angew. Chem. Int. Ed. 2023, 63, e202312383. DOI: 10.1002/anie.202312383).

Shun-Jun Li and Yingsheng Zhao of Soochow University assembled the α-cyano ester 22 via the Ru-catalyzed coupling of the α-bromo cyanoacetate 21 with the aniline derivative 20 (Chem. Eur. J. 2023, 29, e202300905. DOI: 10.1002/chem.202300905). Benjamin List, also of the Max-Planck Institut für Kohlenforschung, used an imidodiphosphorimidate to mediate the coupling of the N,O-acetal 24 with anisole 23, leading to the α-aryl glycine ester 25 in high ee (J. Am. Chem. Soc. 2023, 145, 15708. DOI: 10.1021/jacs.3c05148). Shu-Li You, also of the Shanghai Institute of Organic Chemistry, devised the enantioselective Rh-catalyzed conjugate addition of the benzamide 26 to the nitroalkene 27, leading to the ortho-coupled product 28 (ACS Catal. 2023, 13, 8838. DOI: 10.1021/acscatal.3c02199). Peng Liu of the University of Pittsburgh and Yang Yang of the University of California, Santa Barbara also reported high ee in the enzyme-mediated cyclization of the α-bromo amide 29 to the oxindole 30 (Nature Catal. 2023, 6, 628. DOI: 10.1038/s41929-023-00986-5).

Jeremy Robertson of the University of Oxford reported the preparation of the phenol 32 by the α-methylenation of the cyclohexenone 31 followed by rearrangement (Org. Lett. 2023, 25, 7507. DOI: 10.1021/acs.orglett.3c02796). Adriaan J. Minnaard of the University of Groningen assembled the benzaldehyde derivative 35 by combining the chitin-derived furan 33 with ethyl acrylate 34 (Org. Biomol. Chem. 2023, 21, 8372. DOI: 10.1039/D3OB01461D).

Fumimycin (39), isolated from Aspergillus fumisynnematus, showed anti-bacterial and anti peptide deformylase activity. Chang Guo of the University of Science and Technology of China assembled 39 via the enantioselective oxidative coupling of the alanine derivative 36 with hydroquinone 37 to give 38 (Nature Commun. 2023, 14, 6749. DOI: 10.1038/s41467-023-42603-w).

D. F. Taber, Org. Chem. Highlights 2024, June 10.