Sommer Heiko, Weissbrod Tal, Marek Ilan
Schulich Faculty of Chemistry, Technion-Israel Institute of Technology, Technion City, Haifa, 32000, Israel.
ACS Catal. 2019 Mar 1;9(3):2400-2406. doi: 10.1021/acscatal.9b00118. Epub 2019 Feb 5.
An iridium-catalyzed tandem olefin migration/Cope rearrangement of alkenyl ω-ene cyclopropanes is reported. By this means, a variety of complex annulenes are obtained as single diastereomers starting from cyclopropyl ester derived from simple 1,ω-dienes and alkenyldiazo compounds. Long-range olefin migration over up to 10 positions could be realized and coupled with an efficient Cope rearrangement to yield valuable scaffolds. Various functional groups are well-tolerated, giving rise to densely functionalized products. Furthermore, the present methodology could be successfully extended to yield bicyclic cycloheptenones starting from readily available alkenyl cyclopropanols via a Kulinkovich reaction.
报道了一种铱催化的链烯基ω-烯环丙烷的串联烯烃迁移/Cope重排反应。通过这种方法，从简单的1,ω-二烯和链烯基重氮化合物衍生的环丙基酯出发，可得到多种复杂的轮烯作为单一非对映异构体。可实现长达10个位置的远程烯烃迁移，并与高效的Cope重排反应相结合，以生成有价值的骨架结构。各种官能团具有良好的耐受性，从而得到官能团密集的产物。此外，通过Kulinkovich反应，本方法可以成功扩展到从易得的链烯基环丙醇出发制备双环环庚烯酮。
