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Monday, October 24, 2022
Douglass F. Taber
University of Delaware

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

Yasuharu Yoshimi of the University of Fukui devised a photocatalyst that efficiently promoted the coupling of the acid 1 with acrylonitrile 2, to give, with the net addition of two carbons, the nitrile 3 (J. Org. Chem. 2022, 87, 7405. ). Kounosuke Oisaki and Motomu Kanai of the University of Tokyo added a germanium catalyst to promote the coupling of the primary amine 4 with methyl methacrylate 5, leading to the γ-lactam 6 (Org. Lett. 2022, 24, 3325. ). Julien C. Vantourout of the Université Lyon 1 showed that the coupling of the alkene 7 with the ketone 8 to give 9 could be driven by electrolysis, making the Mn(OAc)3 catalytic (J. Org. Chem. 2022, 87, 5690. ). Takuya Suga and Yutaka Ukaji of Kanazawa University activated the alcohol 10 with the Ti complex 11, to give an intermediate that could be added in a conjugate sense to acrylonitrile 2, leading to the nitrile 12 (Angew. Chem. Int. Ed. 2022, 61, e202112533. ).

Giovanni W. Amarante of the Federal University of Juiz de Fora and Fernando Coelho of the University of Campinas developed an improved protocol for the Morita-Baylis-Hillman coupling, allowing the assembly of the alcohol 15 by the addition of the enone 14 to the aldehyde 13 (Eur. J. Org. Chem. 2022, e202101448. ). The late Robert H. Grubbs of Caltech developed a bulky Ru catalyst that effected the Z-selective cross metathesis of the acrylate 17 with the alkene 16, to give 18 (Angew. Chem. Int. Ed. 2022, 61, e202113089. ). Ming Yan of Sun Yat-sen University devised the coupling with 20 and subsequent fragmentation that opened the carboxamide 19 to the alkene 21 (Org. Lett. 2022, 24, 536. ). Aaron D. Sadow of Iowa State University optimized the enyne metathesis of the alkyne 22 with ethylene to give the diene 23 (ACS Catal. 2022, 12, 226. ).

Shouyun Yu of Nanjing University coupled the glycosyl bromide 24 with the bromoalkyne 25 to give the C-alkynyl glycoside 26 (Org. Lett. 2022, 24, 364. ). Isaac J. Krauss of Brandeis University devised conditions for the non-epimerizing conversion of the aldehyde 27 with the Ohira reagent 28 to the alkyne 29 (J. Org. Chem. 2022, 87, 3841. ).

Zhaobin Wang of Westlake University assembled the enantiomerically-enriched allene 32 by the addition of the racemic propargylic bromide 31 to the aldehyde 30 (Angew. Chem. Int. Ed. 2022, 61, e202117114. ). Liang-Qiu Lu of Central China Normal University combined the enone 33 with the cyclic carbonate 34 to give the allene 35 (Angew. Chem. Int. Ed. 2022, 61, e202117215. ).

Scabrolide A (39), isolated from the soft coral Sinularia scabra, inhibits both IL-6 and IL-12, and shows only moderate cyotoxicity. Alois Fürstner of the Max-Planck-Institut für Kohlenforschung devised a convergent route to 39, based on the coupling of the allylic chloride 36 with the sulfide 37 to give 38 (J. Am. Chem. Soc. 2022, 144, 1528. ).

D. F. Taber, Org. Chem. Highlights 2022, October 24.