Organic Chemistry Portal
Organic Chemistry Highlights

Monday, January 27, 2020
Douglass F. Taber
University of Delaware

Functional Group Interconversion: The Raghavan synthesis of Solandelactone F

Song Lin of Cornell University rearranged the epoxide 1 to the corresponding allylic alcohol 2 (J. Am. Chem. Soc. 2019, 141, 9548. DOI: 10.1021/jacs.9b04993). Robert R. Knowles of Princeton University effected the fragmentation of 3 to the formate 4 (J. Am. Chem. Soc. 2019, 141, 1457. DOI: 10.1021/jacs.8b12552). Hye-Young Jang of Ajou University converted the primary amine 5 directly to the alcohol 6 (Eur. J. Org. Chem. 2019, 1940. DOI: 10.1002/ejoc.201900042). Ross M. Denton of the University of Nottingham developed 8 as an effective catalyst for the Mitsunobu coupling of 7 with 2,4-dinitrobenzoic acid to give 9 (Science 2019, 365, 910. DOI: 10.1126/science.aax3353).

Louis C. Morrill of Cardiff University used a borrowed hydrogen strategy to convert 10 to 11 (J. Org. Chem. 2019, 84, 3715. DOI: 10.1021/acs.joc.9b00203). Taiga Yurino and Takeshi Ohkuma of Hokkaido University optimized the coupling of 12 with trimethylsilyl cyanide, leading to the isonitrile 13 (ACS Catal. 2019, 9, 4434. DOI: 10.1021/acscatal.9b00858). Paul Knochel of the Ludwig-Maximilians-Universität München prepared 16 by coupling 14 with 15 (Org. Lett. 2019, 21, 494. DOI: 10.1021/acs.orglett.8b03787). Aigars Jirgensons of the Latvian Institute of Organic Synthesis used strong acid to open the cyclopropane 17, trapping the resulting carbocation with acetonitrile to give 18 (J. Org. Chem. 2019, 84, 3780. DOI: 10.1021/acs.joc.8b02576).

Lanny S. Liebeskind of Emory University assembled the ester 21 by combining the alcohol 19 with the acid 20 in the presence of a diselenide catalyst (J. Org. Chem. 2019, 84, 4954. DOI: 10.1021/acs.joc.8b02765). Jeyakumar Kandasamy of the Indian Institute of Techology, Varanasi used t-butylnitrite to activate the secondary amide 22, coupling the product in the same pot with the amine 23 to give 24 (Org. Biomol. Chem. 2019, 17, 845. DOI: 10.1039/C8OB03010C). Praveen P. Singh of the United College of Engineering and Research established a photoredox strategy for preparing 27 by the coupling of 25 with 26 (Tetrahedron Lett. 2019, 60, 40. DOI: 10.1016/j.tetlet.2018.11.050). Xi-Cun Wang of Northwest Normal University showed that the oxidation of 28 was selective, leading to the sulfonamide 29 (Tetrahedron 2019, 75, 2763. DOI: 10.1016/j.tet.2019.03.047).

Solandelactone F (33) is an oxylipin isolated from the sea fan Solanderia secunda. In the course of a synthesis of 33, Sadagopan Raghavan of the Indian Institute of Chemical Technology oxidized the sulfide 30 to the corresponding sulfoxide, that rearranged in the presence of 31 to the enone 32 (Org. Biomol. Chem. 2019, 17, 4572. DOI: 10.1039/C9OB00623K).

D. F. Taber, Org. Chem. Highlights 2020, January 27.