Achard Mathieu, Tenaglia Alphonse, Buono Gérard
Laboratoire de Synthèse Asymétrique, UMR 6180 CNRS Chirotechnologies: Catalyse et Biocatalyse, Université d'Aix-Marseille P. Cézanne, Faculté des Sciences et Techniques de St. Jérôme, EGIM, 13397 Marseille, France.
Org Lett. 2005 Jun 9;7(12):2353-6. doi: 10.1021/ol050618j.
[reaction: see text] The CoI2(dppe)/Zn/ZnI2 system effectively catalyzes the [6 + 2] cycloaddition of cycloheptatriene with terminal alkynes to afford 7-alkyl-bicyclo[4.2.1]nona-2,4,7-trienes in fair to excellent yields. The catalyst proved to be tolerant toward functional groups such as ketone, sulfone, ester, ketal, ether, alcohol, imide, and nitrile. The enantioselective cycloaddition of CHT and phenylacetylene with BINOL phosphoramidite ligand 4 afforded the cycloadduct 3a (R = Ph) in 91% yield and 74% ee.
[反应：见正文] CoI₂(dppe)/Zn/ZnI₂体系能有效催化环庚三烯与末端炔烃的[6 + 2]环加成反应，以中等至优异的产率得到7-烷基-双环[4.2.1]壬-2,4,7-三烯。该催化剂对酮、砜、酯、缩酮、醚、醇、酰亚胺和腈等官能团具有耐受性。环庚三烯（CHT）与苯乙炔在联萘酚亚磷酰胺配体4存在下进行对映选择性环加成反应，以91%的产率和74%的对映体过量值得到环加成产物3a（R = Ph）。
