雙烯三羰鐵分子內自由基環化反應之範圍與限制
碩士 === 國立臺灣師範大學 === 化學學系 === 86 === Reaction of (η5-2-methoxy-peatadienyl)Fe(CO)3 cation salts and (η5-2-methoxy-cyclohexadienyl)Fe(CO)3 cation salts with functionalized zinc-copper reagents [IZn(CN)Cu(CH2)nCO2Et] afforded neutral (η4-2-methoxy-pentadienyl)Fe(CO)3 complexes and (η4-2-methoxy-cy...
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| Format: | Others |
| Language: | zh-TW |
| Published: |
1998
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| Online Access: | http://ndltd.ncl.edu.tw/handle/20687035675383621008 |
| Summary: | 碩士 === 國立臺灣師範大學 === 化學學系 === 86 ===
Reaction of (η5-2-methoxy-peatadienyl)Fe(CO)3 cation salts and (η5-2-methoxy-cyclohexadienyl)Fe(CO)3 cation salts with functionalized zinc-copper reagents [IZn(CN)Cu(CH2)nCO2Et] afforded neutral (η4-2-methoxy-pentadienyl)Fe(CO)3 complexes and (η4-2-methoxy-cyclohexadienyl)Fe(CO)3 complexes with an ester functional group side chains at the terminal position of the diene ligands.
The ester functional group was transformed into acid functional group by reaction with 6 molar equiv of aqueous KOH in 1:1 MeOH/THF solution.
Addition of 2.5 molar equiv of MeLi to the acid complexs at 0℃ provided the methyl ketone devivative in moderated yields.
Samarium diiodide (SmI2) induced intramolecular radical cyclization of the ketyl radical at the terminal position of the diene ligand generated cyclopetanol and cyclohexanol derivatives under mild reaction conditions. The scope and limitation of the radical cyclization will be discussed.
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