Iridium-catalyzed allylic vinylation and asymmetric allylic amination reactions with o-aminostyrenes.
Iridium-catalyzed allylic vinylation and asymmetric allylic amination reactions with o-aminostyrenes.
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DOI：
10.1021/ja2092954
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发表时间：
2011-11
影响因子：
15
通讯作者：
Keyin Ye;H. He;Wen-Bo Liu;L. Dai;G. Helmchen;S. You
中科院分区：
文献类型：
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作者：
Keyin Ye;H. He;Wen-Bo Liu;L. Dai;G. Helmchen;S. You
本文实现了羰基烯丙酯与邻氨基苯乙烯衍生物的烯丙基乙烯化反应，得到了跳过的（Z，E）-二烯衍生物。以(E)-丁-2-烯-1,4-二烷基二碳酸二甲酯为底物，通过ir催化的多米诺烯丙基乙烯化/分子内烯丙基胺化反应，高效地对映选择性合成了1-苯氮卓衍生物。对烯丙基乙烯化反应进行了机理研究，结果表明，烯丙基前体的离去基在指导反应途径中起着关键作用。各种烯丙基前驱体的筛选表明，铁催化的烯丙基磷酸二乙酯与邻氨基苯乙烯衍生物的反应是通过烯丙基胺化途径进行的。胺化产物的闭合复合反应（RCM）产生了一系列对映体富集的1,2-二氢喹啉衍生物。它们的效用由(-)-angustureine的不对称全合成表明。
An Ir-catalyzed allylic vinylation reaction of allyl carbonates with o-aminostyrene derivatives has been realized, providing skipped (Z,E)-diene derivatives. With (E)-but-2-ene-1,4-diyl dimethyl dicarbonate as the substrate, an efficient enantioselective synthesis of 1-benzazepine derivatives via an Ir-catalyzed domino allylic vinylation/intramolecular allylic amination reaction has been developed. Mechanistic studies of the allylic vinylation reaction have been carried out, and the results suggest that the leaving group of the allylic precursor plays a key role in directing the reaction pathway. Screening of various allylic precursors showed that Ir-catalyzed reactions of allyl diethyl phosphates with o-aminostyrene derivatives proceed via an allylic amination pathway. A subsequent ring-closing metathesis (RCM) reaction of the amination products led to a series of enantiomerically enriched 1,2-dihydroquinoline derivatives. Their utility is indicated by an asymmetric total synthesis of (-)-angustureine.