Chen Peng-Hao, Sieber Joshua, Senanayake Chris H, Dong Guangbin
The University of Texas at Austin, Department of Chemistry, Austin, TX 78712, United States.
Department of Chemical Development, Boehringer Ingelheim Pharmaceuticals, Inc., 900 Ridgebury Road/P.O. Box 368, Ridgefield, Connecticut 06877-0368, United States.
Chem Sci. 2015 Oct 1;6(10):5440-5445. doi: 10.1039/C5SC01875G. Epub 2015 Jul 10.
Here we report a reagent-free rhodium-catalyzed ring-expansion reaction via C-C cleavage of cyclobutenones. A variety of poly-substituted cyclopentenones and 1-indanones can be synthesized from simple cyclobutenones and benzocyclobutenones. The reaction condition is near pH neutral without additional oxidants or reductants. The potential for developing a dynamic kinetic asymmetric transformation of this reaction has also been demonstrated. Further study supports the proposed pathway involving Rh-insertion into the cyclobutenone C-C bond, followed by β-hydrogen elimination, olefin insertion and reductive elimination.
在此，我们报道了一种通过环丁烯酮的碳-碳键裂解实现的无试剂铑催化扩环反应。多种多取代环戊烯酮和1-茚酮可由简单的环丁烯酮和苯并环丁烯酮合成。反应条件接近中性pH，无需额外的氧化剂或还原剂。该反应动态动力学不对称转化的潜力也得到了证明。进一步的研究支持了所提出的反应途径，即铑插入环丁烯酮的碳-碳键，随后进行β-氢消除、烯烃插入和还原消除。
