Organic Chemistry Portal
Organic Chemistry Highlights

Monday, September 9, 2019
Douglass F. Taber
University of Delaware

Carbon-Carbon Bond Formation: The Fürstner Synthesis of Pateamine A

Yuanhong Liu of the Shanghai Institute of Organic Chemistry developed a reagent combination that converted even a secondary alkyl chloride 1 to the corresponding nitrile 2 (Org. Lett. 2018, 20, 7735. DOI: 10.1021/acs.orglett.8b03539). Denis Chusov of the Nesmeyanov Institute of Organoelements Compounds coupled 4 with the ketone 3, leading to the nitrile 5 (Org. Biomol. Chem. 2018, 16, 7693. DOI: 10.1039/C8OB01992D). Luo Yang of Xiangtan University prepared 8 by adding the alkyl radical from decarbonylation of 6 to the diester 7 (Tetrahedron Lett. 2018, 59, 2934. DOI: 10.1016/j.tetlet.2018.06.042). Ilhyong Ryu of Osaka Prefecture University and Yen-Ku Wu of the National Chiao Tung University observed substantial quantities of the homodimer 10 from irradiation of the iodide 9 (Chem. Commun. 2018, 54, 5582. DOI: 10.1039/C8CC02445F). This could offer a practical alternative to the classic Kolbe coupling.

Yoshitaka Hamashima of the University of Shizuoka established microwave flow conditions for the Johnson-Claisen combination of 11 with 12 to give 13 (Org. Process Res. Dev. 2018, 22, 1029. DOI: 10.1021/acs.oprd.8b00185). Marc Mauduit of the Institute of Chemical Sciences of Rennes (ISCR) devised a simple Ru catalyst that mediated the cross metathesis of 14 with 15, leading to the Z alkene 16 (Org. Lett. 2018, 20, 6822. DOI: 10.1021/acs.orglett.8b02943). Feng Liu of Soochow University assembled 20 by activating 17 with 18, then adding that intermediate to 19 (Org. Chem. Front. 2018, 5, 3443. DOI: 10.1039/C8QO01046C). Aijun Lin and Hequan Yao of China Pharmaceutical University observed high regioselectivity in the synthesis of 23 by the addition of the cyclopropanol 22 to the ester 21 (Adv. Synth. Catal. 2018, 360, 3171. DOI: 10.1002/adsc.201800200).

Bruno V. M. Teodoro of the Universidade de São Paulo prepared 26 by adding vinyl magnesium bromide to 24 followed by 25 (J. Org. Chem. 2018, 83, 13604. DOI: 10.1021/acs.joc.8b02251). Magnus Rueping of RWTH Aachen established that the intermediate from the cyclization of 27 added to 28 to give the γ-lactam 29 (Chem. Eur. J. 2018, 24, 14054. DOI: 10.1002/chem.201802907).

Karl Anker Jørgensen of Aarhus University showed that the Hayashi secondary amine catalyst effectively mediated the enantioselective addition of 31 to 30, to assemble the allene 32 (Angew. Chem. Int. Ed. 2018, 57, 10661. DOI: 10.1002/anie.201806238). Varinder K. Aggarwal of the University of Bristol added 34 to 33 to give the stereodefined allylic boronic ester. Via syn or anti elimination, this could then be directed to either enantiomer of the allene 35 (Angew. Chem. Int. Ed. 2018, 57, 8203. DOI: 10.1002/anie.201804446).

Pateamine A (38) and its simpler congeners demonstrate remarkable antineoplastic activity. Alois Fürstner of the Max-Planck-Institut für Kohlenforschung assembled the dienoic acid of 38 by the Fe-catalyzed coupling of 36 with CH3MgBr to give 37 (J. Am. Chem. Soc. 2018, 140, 10514. DOI: 10.1021/jacs.8b05094).

D. F. Taber, Org. Chem. Highlights 2019, September 9.