Conjugate Additions and Transposition of the Allylic Alcohols of Enol Ethers of 1, 2-Cyclohexanedione.

Publication Year:
2010
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Repository URL:
https://dc.etsu.edu/etd/1748; https://dc.etsu.edu/cgi/viewcontent.cgi?article=3103&context=etd
Author(s):
Otoo, Barnabas
Tags:
α; β-unsaturated systems; enone; enolate; silane; transposition; nucleophile; Chemistry; Organic Chemistry; Physical Sciences and Mathematics
thesis / dissertation description
A variety of protected enolic forms of 1, 2-cyclohexanedione was prepared as substrates for conjugate addition studies using organocopper reagents. The sequence involved the enol ether preparation via the enolate, alkylation with an organometalic reagent, and oxidative rearrangement with pyridinium chlorochromate followed by the conjugate addition reactions. Protection of 1, 2-cyclohexanedione was achieved by reacting with chloro tert-butyldimethyl silane and subjected to alkylation. Steric problems were encountered and so an alternative protective group the methoxymethyl acetal was prepared and studied. Alkylation of these derivatives was successful; however, the oxidation was problematic and although evidence for rearrangement was observed in one case, it did not provide the desired ketone.