Construction of carbon frameworks through β-carbon elimination mediated by transition metals
Construction of carbon frameworks through β-carbon elimination mediated by transition metals
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DOI：
10.1246/bcsj.79.1315
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发表时间：
2006-09-15
影响因子：
4
通讯作者：
Matsuda, Takanori
中科院分区：
文献类型：
--
作者：
Murakami, Masahiro;Makino, Masaomi;Matsuda, Takanori
我们的实验室开发了过渡金属环丁醇盐进行β-碳消除的新催化反应。通过将芳基铑 (I) 物质加成到环丁酮中生成的环丁醇铑 (I) 经过 β-碳消除，导致四元碳环骨架开环。通过β-碳消除开环过程的合成潜力已通过其在形成七元环的扩环反应中的应用得到证明。此外，通过将环丁酮和炔烃在镍(0)上的氧化环化与所得环丁醇镍(II)中的β-碳消除相结合，实现了炔烃正式插入环丁酮骨架中。
New catalytic reactions in which transition-metal cyclobutanolates undergo beta-carbon elimination have been developed in our laboratory. Rhodium(I) cyclobutanolate generated by the addition of an arylrhodium(I) species to a cyclobutanone undergoes beta-carbon elimination to cause ring opening of the four-membered carbocyclic framework. The synthetic potential of the ring-opening process through beta-carbon elimination has been demonstrated by its application to a ring-expansion reaction forming a seven-membered ring. Furthermore, a formal alkyne insertion into the cyclobutanone framework is achieved by combining oxidative cyclization of a cyclobutanone and an alkyne on nickel(0) and beta-carbon elimination from the resulting nickel(II) cyclobutanolate.