Cheng Qing-Qing, Yedoyan Julietta, Arman Hadi, Doyle Michael P
Department of Chemistry, The University of Texas at San Antonio, One UTSA Circle, San Antonio, TX, 78249, USA.
Angew Chem Int Ed Engl. 2016 Apr 25;55(18):5573-6. doi: 10.1002/anie.201601260. Epub 2016 Mar 23.
A dirhodium(II)-catalyzed annulation reaction between two structurally different diazocarbonyl compounds furnishes the donor-acceptor cyclopropane-fused benzoxa[3.2.1]octane scaffold with excellent chemo-, regio-, and diastereoselectivity under exceptionally mild conditions. The composite transformation occurs by [3+2]-cycloaddition between donor-acceptor cyclopropenes generated from enoldiazoacetamides and carbonyl ylides formed from intramolecular carbene-carbonyl cyclization in one pot with one catalyst. The annulation products can be readily transformed into benzoxa[3.3.1]nonane and hexahydronaphthofuran derivatives with exact stereocontrol. This method allows the efficient construction of three fused and bridged ring systems, all of which are important skeletons of numerous biologically active natural products.
在异常温和的条件下，一种二价铑（II）催化的两种结构不同的重氮羰基化合物之间的环化反应，以优异的化学、区域和非对映选择性提供了供体-受体环丙烷稠合的苯并氧杂[3.2.1]辛烷骨架。这种复合转化是通过由烯醇重氮乙酰胺生成的供体-受体环丙烯与由分子内卡宾-羰基环化在一锅法中用一种催化剂形成的羰基叶立德之间的[3+2]环加成反应发生的。环化产物可以很容易地在精确的立体控制下转化为苯并氧杂[3.3.1]壬烷和六氢萘并呋喃衍生物。该方法允许高效构建三个稠合和桥连的环系统，所有这些都是众多生物活性天然产物的重要骨架。
