State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai 200032, China.
J Am Chem Soc. 2011 Nov 23;133(46):19006-14. doi: 10.1021/ja2092954. Epub 2011 Nov 2.
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.
已实现了 Ir 催化的烯丙基碳酸酯与邻氨基苯乙烯衍生物的烯丙基乙烯基化反应，提供了（Z，E）-二烯衍生物。以（E）-丁-2-烯-1,4-二基二甲酸二甲酯为底物，通过 Ir 催化的串联烯丙基乙烯基化/分子内烯丙基胺化反应，高效地对 1-苯并氮杂卓衍生物进行了对映选择性合成。对烯丙基乙烯基化反应进行了机理研究，结果表明，烯丙基前体的离去基团在控制反应途径方面起着关键作用。对各种烯丙基前体的筛选表明，Ir 催化的邻氨基苯乙烯衍生物与二乙基膦酸烯丙酯的反应通过烯丙基胺化途径进行。随后对胺化产物进行闭环复分解（RCM）反应，得到一系列对映体富集的 1,2-二氢喹啉衍生物。通过（-）-angustureine 的不对称全合成表明了它们的实用性。
