A Benzyne Insertion Approach to Hetisine-Type Diterpenoid Alkaloids: Synthesis of Cossonidine (Davisine).

Autor: Kou KGM; Department of Chemistry , University of California, Berkeley , Berkeley , California 94720 , United States., Pflueger JJ; Department of Chemistry , University of California, Berkeley , Berkeley , California 94720 , United States., Kiho T; Department of Chemistry , University of California, Berkeley , Berkeley , California 94720 , United States., Morrill LC; Department of Chemistry , University of California, Berkeley , Berkeley , California 94720 , United States., Fisher EL; Department of Chemistry , University of California, Berkeley , Berkeley , California 94720 , United States., Clagg K; Department of Chemistry , University of California, Berkeley , Berkeley , California 94720 , United States., Lebold TP; Department of Chemistry , University of California, Berkeley , Berkeley , California 94720 , United States., Kisunzu JK; Department of Chemistry & Biochemistry , Colorado College , Colorado Springs , Colorado 80903 , United States., Sarpong R; Department of Chemistry , University of California, Berkeley , Berkeley , California 94720 , United States.
Jazyk: angličtina
Zdroj: Journal of the American Chemical Society [J Am Chem Soc] 2018 Jul 05; Vol. 140 (26), pp. 8105-8109. Date of Electronic Publication: 2018 Jun 19.
DOI: 10.1021/jacs.8b05043
Abstrakt: The hetisine-type natural products exhibit one of the most complex carbon skeletons within the diterpenoid alkaloid family. The use of network analysis has enabled a synthesis strategy to access alkaloids in this class with hydroxylation on the A-ring. Key transformations include a benzyne acyl-alkylation to construct a key fused 6-7-6 tricycle, a chemoselective nitrile reduction, and sequential C-N bond formations using a reductive cyclization and a photochemical hydroamination to construct an embedded azabicycle. Our strategy should enable access to myriad natural and unnatural products within the hetisine-type.
Databáze: MEDLINE
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