Dialkoxyethylidene and .eta.2-1,2-dialkoxyethylene iron compounds as 2 carbon templates for generating acetaldehyde and a glycolaldehyde ether
| Autor: | Edward J. Crawford, Alan R. Cutler, Thomas Bodnar |
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| Rok vydání: | 1986 |
| Předmět: | |
| Zdroj: | Journal of the American Chemical Society. 108:6202-6212 |
| ISSN: | 1520-5126 0002-7863 |
| DOI: | 10.1021/ja00280a016 |
| Popis: | Full details on the preparation and characterization of the ..cap alpha..-ethoxy-..beta..-methoxyethylidene Fp 5, on its irreversible isomerization to the eta/sup 2/-1,2-methoxyethoxyethylene Fp salt 6, and on its reduction to the ..cap alpha..-ethoxy-..beta..-methoxyethyl Fp 17 are presented. Other examples of cis-1,2-dialkoxyethylene Fp salts also are synthesized. The dimethoxy example 11 upon hydrolysis gives the ..cap alpha..-methoxyformylmethyl Fp complex 14, whereas reducing it gives the ..cap alpha..,..beta..-dimethoxyethyl complex 18. Both spectroscopically characterized ..cap alpha..,..beta..-dialkoxyethyl complexes afford eta/sup 2/-vinyl ether Fp compounds 19 (R = CH/sub 3/) and 20 (R = CH/sub 2/CH/sub 3/) upon treating with Ph/sub 3/C/sup +/PF/sub 6//sup -/. ..beta..-Methoxide abstraction from 18 predominates. Hydrolysis of 19 then gives FpCH/sub 2/CHO 15, which after treating with acid and iodide yields acetaldehyde. The ..cap alpha..-methoxyformylmethyl 14, in turn, gives methoxyacetaldehyde. Thus, coordinated ligand reactions are presented that use the methoxyacetyl ligand on FpCOCH/sub 2/OCH/sub 3/ (4) as a C/sub 2/ template in selectively incorporating both of these skeletal carbon centers into either acetaldehyde or methoxyacetaldehyde. |
| Databáze: | OpenAIRE |
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