Carbocyclization versus Oxycyclization on the Metal-Catalyzed Reactions of Oxyallenyl C3-Linked Indoles

被引:40
作者
Alcaide, Benito [1 ]
Almendros, Pedro [2 ]
Alonso, Jose M. [1 ]
Fernandez, Israel [3 ]
机构
[1] Univ Complutense Madrid, Fac Quim, Dept Quim Organ 1,CSIC, Grp Lactamas & Heterociclos Bioact,Unidad Asociad, E-28040 Madrid, Spain
[2] CSIC, Inst Quim Organ Gen, IQOG, E-28006 Madrid, Spain
[3] Univ Complutense Madrid, Fac Quim, Dept Quim Organ 1, E-28040 Madrid, Spain
关键词
ANTITUMOR-ACTIVITY; ALLENYL KETONES; GOLD CATALYSIS; CYCLIZATION; REACTIVITY; ALKALOIDS; FUNCTIONALIZATION; GOLD(III); POTENT; CYCLOISOMERIZATION;
D O I
10.1021/jo401013d
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
The preparation of previously unknown (indol-3-yl)-alpha-allenols and -allenones was accomplished from indole-3-carbaldehydes, through indium mediated Barbier allenylation reaction taking advantage of the N-(2-pyridyl)sulfonyl group. Metal catalyzed cyclizations of oxyallenyl C3-linked indoles proceeded in two ways depending on the presence or absence of the N- (2-pyridyl)sulfonyl group. For allenols, gold catalyzed oxycyclization occurred in the presence of the protecting group; in the absence of the protecting group, palladium- and gold-catalyzed benzannulations operated. On the contrary, under gold catalysis furyl-indoles were obtained as exclusive products from NH-allenones, while S-endo carbocyclization adducts were the major components starting from N-SO(2)py-protected allenones. These cyclization reactions have been developed experimentally, and their mechanisms have additionally been investigated by a computational study.
引用
收藏
页码:6688 / 6701
页数:14
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