| Summary: | 博士 === 國立師範大學 === 化學學系 === 83 === A variety of highly functionalized zinc-copper reagents
RCu(CN)ZnI react regio- and stereospecifically with Dicarbonyl
(η5-cyclopentadienyl)(η4-cyclohexa-1,3-diene)molybdenum cation to generate
neutral Dicarbonyl (η5-cyclopentadienyl)(η3-allyl)molybdenum complexes with a
functionalized side-chain at the C-4 position of the ring. Deproction of
complexes followed by intramolecular cyclization using NOBF4 gave fused
bicyclo[4.4.0]decene derivatives containing an oxygen, nitrogen or sulfur atom
at the C-2 position of the rings.
The addition of a variety of highly functionalized znic-copper reagents
RCu(CN)ZnI to (tropylium)Cr(CO)3 cation gives
(η6-cyclohepta-1,3,5-triene)Cr(CO)3 complexes with a functionalized side-chain
at the C-7 position of the ring.Intramolecular cyclization of ester-substituted
adducts using lithium diisopropylamide generates fused bicyclo[5.3.0]decane
and -[5.4.0]undecane derivatives.
Benzyl alcohol chromium tricarbonyl complex was prepared in 75% yield by
treatmentreatment of chromium hexcarbonyl and benzyl alcohol in dibutyl
ether/tetrahydrofuran (10:1) under nitrogen.Reaction of benzyl alcohol chromium
tricarbonyl with concentrated hydrochloric acid gave benzyl chloride chromium
tricarbonyl(75%). the nucleophilic substitution reaction of a variety of amino
acid derivatives with benzyl chloride chromium tricarbonyl generated chromium
complexes with an amino acid derivative at the benzyl position.Intramolecular
cyclization of the complex using lithium hexamethyldisilazide followed by
oxidation with I2 led to fused bicyclic products.
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