New picropodophyllin analogs via palladium-catalyzed allylic alkylation - Hiyama cross-coupling sequences

被引:31
作者
Vitale, Maxime [1 ]
Prestat, Guillaume [1 ]
Lopes, David [1 ]
Madec, David [1 ]
Kammerer, Claire [1 ]
Poli, Giovanni [1 ]
Girnita, Leonard [2 ]
机构
[1] Univ Paris 06, UPMC, CNRS, Chim Organ Lab,FR2769 Inst Chim Mol,UMR 7611, F-75005 Paris, France
[2] Karolinska Inst, Stockholm, Sweden
关键词
D O I
10.1021/jo800707q
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
Unsaturated malonyl esters underwent Pd-catalyzed intramolecular allylic alkylation to give 4-vinyl-substituted gamma-lactones. In contrast to the formerly studied cyclization of malonamides, this reaction could be achieved only with a substrate incorporating a suitably positioned silicon moiety, which directs the ionization toward the desired eta(3)-allyipalladium complex. The resulting 4-[dimethyl-(2-thienyl)silylvinyl]lactone could be subsequently engaged into Hiyama couplings with various iodoarenes, to give the corresponding 4-(alpha-styryl)-gamma-lactones. The use of a specifically substituted iodoarene generated an advanced tetracyclic lactone intermediate incorporating rings A-D of lignans belonging to the podophyllotoxin family. Subsequent electrophilic aromatic substitution with a variety of electron-rich arenes afforded the target picropodophyllin analogs.
引用
收藏
页码:5795 / 5805
页数:11
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