类叶立德型亚锗烯对末端炔烃的显著反应性：[4+2]环加成与C-H键活化

Striking reactivity of ylide-like germylene toward terminal alkynes: [4+2] cycloaddition versus C-H bond activation.

作者信息

Yao Shenglai, van Wüllen Christoph, Driess Matthias

机构信息

Technische Universität Berlin, Institute of Chemistry: Metalorganics and Inorganic Materials, Sekr. C2, Strasse des 17. Juni 135, Berlin, Germany.

出版信息

Chem Commun (Camb). 2008 Nov 14(42):5393-5. doi: 10.1039/b811952j. Epub 2008 Sep 18.

DOI:10.1039/b811952j

PMID:18985221

Abstract

The isolable ylide-like N-heterocyclic germylene LGe: (2) {L = CH[(C=CH(2))CMe]N(aryl), aryl = 2,6-(i)Pr(2)C(6)H(3)} shows an unprecedented dual reactivity toward terminal alkynes: its reaction with acetylene leads via [4+2] cycloaddition to the novel intramolecular donor stabilised germylene 3, while conversion of phenylacetylene furnishes the analogous cycloadduct 4 along with a C-H bond activation product, the novel N-donor stabilised alkynyl germylene 5.

摘要

可分离的类叶立德型氮杂环锗烯LGe: (2) {L = CH[(C=CH(2))CMe]N(芳基)，芳基 = 2,6-(异丙基)2C6H3}对末端炔烃表现出前所未有的双重反应性：它与乙炔通过[4+2]环加成反应生成新型分子内供体稳定的锗烯3，而苯乙炔的转化则产生类似的环加成产物4以及一个C-H键活化产物，即新型氮供体稳定的炔基锗烯5。