Stereospecific synthesis of dienone iron tricarbonyl complexes by friedelcrafts acylation |
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Authors: | Robert E. Graf C. Peter Lillya |
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Affiliation: | Department of Chemistry, University of Massachusetts, Amherst, Massachusetts 01002 U.S.A. |
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Abstract: | Acylation of diene Fe(CO)3 complexes using the Perrier complexes RCOCl/AlCl3 in methylene chloride at 0°C gives dienone complexes in high yield. Substitution occurs only at unsubstituted terminal carbons of the diene unit. Quenching the reaction mixtures in cold aqueous ammonia gives cis dienone complexes only. Trans dienone complexes are prepared by subsequent isomerization in methanolic sodium methoxide. Formylation of diene Fe(CO)3 complexes proceeds in modest yield using dichloromethylmethyleter/AlCl3 in methylene chloride to give trans-dienal complexes. Reduction of the dienone and dienal complexes as well as those of dienols and dienoic esters with 4 : 1 AlCl3/LiAlH4 results in complete removal of the oxygen function to give trans-diene complexes in good yield. |
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