578714-30-4Relevant academic research and scientific papers
Formation of manganese enediyne complexes from manganese alkynylcarbene complexes
Casey, Charles P.,Dzwiniel, Trevor L.,Kraft, Stefan,Kozee, Michael A.,Powell, Douglas R.
, p. 320 - 326 (2003)
Dimerization of the alkynylcarbene complex (C5H4Me)(CO)2Mn=C(Tol)C≡CTol (10) occurred at 65°C to give a mixture of E- and Z-enediyne complexes [(C5H4Me)(OC)2Mn]2[η 2,η2-TolC≡C(Tol)C=C(Tol)C≡CTol] (13). Thermolysis of alkynye complexes 10 at higher (100°C) temperature led to the formation of manganese-free E- and Z-enediynes TolC≡C(Tol)C=C(Tol)C≡CTol (14-E and 14-Z). Attempted synthesis of the tethered bis-(alkynylcarbene) complex Cp(OC)2Mn=C(Ph)C≡CCH2CH2CH 2C≡CC(Ph)=Mn(CO)2Cp led instead to the cyclic enediyne complex [Cp(OC)2Mn]2[η2,η2- PhC≡CC(CH2CH2CH2)=CC≡CPh] (19), from which the metal-free enediyne 1,2-bis(phenylethynyl)cyclopentene (20) was released by thermolysis at 90°C.
Synthesis of cyclic cis-enediynes from manganese carbyne complexes and α,ω-diynes
Casey, Charles P.,Dzwiniel, Trevor L.,Kraft, Stefan,Guzei, Ilia A.
, p. 3915 - 3920 (2008/10/08)
Cyclic cis-enediynes are readily prepared by a two-step one-pot procedure. The first step is the copper-catalyzed addition of α,ω-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.
