Synthesis of Cyclic <i>cis</i>-Enediynes from Manganese Carbyne Complexes and α,ω-Diynes
                                
                                    
                                        作者:Charles P. Casey、Trevor L. Dzwiniel、Stefan Kraft、Ilia A. Guzei                                    
                                    
                                        DOI:10.1021/om0303799
                                    
                                    
                                        日期:2003.9.1
                                    
                                    Cyclic cis-enediynes are readily prepared by a two-step one-pot procedure. The first step is the copper-catalyzed addition of alpha,omega-diynes to manganese carbyne complexes to give intermediate bis(alkynylcarbene) complexes that rearrange to enediyne complexes below room temperature. In the second step, the free enediyne is released from manganese by photolysis, copper-catalyzed air oxidation, or stoichiometric Cu(II) oxidation. These new procedures have been applied to a variety of five-, six-, and seven-membered-ring cyclic enediynes containing a range of ether, ester, and ketone functional groups.