Wong AR,
Fastuca NJ,
Mak VW,
Kerkovius JK,
Stevenson SM,
Reisman SE.
*
California Institute of Technology, Pasadena, USA
Total Syntheses of the C
19 Diterpenoid Alkaloids (–)-Talatisamine, (–)-Liljestrandisine, and (–)-Liljestrandinine by a Fragment Coupling Approach.
ACS Cent. Sci. 2021;
7: 1311-1316
DOI:
10.1021/acscentsci.1c00540
Key words
aconitine-type alkaloids - Giese reaction - semipinacol rearrangement - (–)-talatisamine - (–)-liljestrandisine
Significance
Reisman and co-workers report a convergent fragment coupling approach to the aconitine-type alkaloids (–)-talatisamine, (–)‑liljestrandisine, and (–)-liljestrandinine. The structure of (–)-liljestrandisine was revised.
Comment
1,2-Addition of lithiated bromide H to ketone D gave I after in situ TMS protection. TMSNTf2 mediated the key semipinacol rearrangement that led to ketone K. This was elaborated to the full carbon skeleton of the natural product in 14 steps.
