Laboratoire de Chimie Organique, ESPCI ParisTech, CNRS (UMR 7084), 10 rue Vauquelin 75231 Paris Cedex 05, France.
Chemistry. 2012 Jun 18;18(25):7810-22. doi: 10.1002/chem.201200566. Epub 2012 May 15.
The gold(I)-catalysed cycloisomerisation of appropriately substituted 1,6-cyclopropene-enes proceeds through regioselective electrophilic ring opening of the three-membered ring to generate an alkenyl gold carbenoid that achieves the intramolecular cyclopropanation of the remote olefin. This strategy allows straightforward, highly efficient and diastereoselective access to a variety of substituted 3-oxa- and 3-azabicyclo[4.1.0]heptanes, as well as to bicyclo[4.1.0]heptan-3-ol derivatives. Since the isopropylidene group in the resulting cycloisomerisation products can be subjected to ozonolysis, 3,3-dimethylcyclopropenes behave as interesting surrogates for α-diazoketones.
金（I）催化的适当取代的 1,6-环丙烯烯的环异构化通过三员环的区域选择性亲电开环进行，生成烯基金卡宾，该卡宾实现了远程烯烃的分子内环丙烷化。该策略允许直接、高效和立体选择性地获得各种取代的 3-氧杂和 3-氮杂双环[4.1.0]庚烷，以及双环[4.1.0]庚烷-3-醇衍生物。由于所得环异构化产物中的异丙叉基可以进行臭氧分解，因此 3,3-二甲基环丙烯是α-重氮酮的有趣替代物。
