TY - JOUR
T1 - Total synthesis and structure revision of the marine metabolite palmerolide A
AU - Jiang, Xin
AU - Liu, Bo
AU - Lebreton, Sylvain
AU - De Brabander, Jef K.
PY - 2007/5/23
Y1 - 2007/5/23
N2 - We describe a highly convergent and flexible synthesis of the novel antarctic marine metabolite palmerolide Aan effort leading to a reformulation of palmerolide A as ent-24, the enantiomer of the C19,C20-bis-epimer of the original proposed structure 1. Our total synthesis features a highly stereoselective vinylogous Mukaiyama aldol reaction to introduce the C19,C20-stereodiad, an efficient Suzuki cross-coupling to install the endocyclic diene unit, and an intramolecular Horner-Wadsworth-Emmons olefination to close the macrocycle. Starting from fragments 2, 3 (ent-3), and 13 (prepared in five to eight steps each, 38-70% overall yield) the synthesis of the proposed structure 1 and the enantiomer of palmerolide A (24) was completed in an additional 14 steps (22 steps longest linear sequence).
AB - We describe a highly convergent and flexible synthesis of the novel antarctic marine metabolite palmerolide Aan effort leading to a reformulation of palmerolide A as ent-24, the enantiomer of the C19,C20-bis-epimer of the original proposed structure 1. Our total synthesis features a highly stereoselective vinylogous Mukaiyama aldol reaction to introduce the C19,C20-stereodiad, an efficient Suzuki cross-coupling to install the endocyclic diene unit, and an intramolecular Horner-Wadsworth-Emmons olefination to close the macrocycle. Starting from fragments 2, 3 (ent-3), and 13 (prepared in five to eight steps each, 38-70% overall yield) the synthesis of the proposed structure 1 and the enantiomer of palmerolide A (24) was completed in an additional 14 steps (22 steps longest linear sequence).
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U2 - 10.1021/ja0715142
DO - 10.1021/ja0715142
M3 - Article
C2 - 17458968
AN - SCOPUS:34249037678
SN - 0002-7863
VL - 129
SP - 6386
EP - 6387
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 20
ER -