Ethers, cyclohexenyl substituted

Abe, T. Hayashi, E. Baba, H. Nagase, S. Synthesis of perfluorohicyclic ethers [2]. The electrochemical fluorination of [a]-cyclohexenyl-substituted carboxylic acid derivatives. J. Fluorine Chem. 1984, 25(4), 419. 

Muthusamy et al. (82) prepared a number of oxacyclic ether compounds from the tandem ylide formation-dipolar cycloaddition methodology. Their approach provides a synthetic tactic to compounds such as ambrosic acid, smitopsin, and linearol. Starting with either cyclopentane or cyclohexane templates, they prepared ylide sizes of five or six, which are trapped in an intermolecular cycloaddition reaction by the addition of DMAD. The products are isolated in good overall yield. In a second system, 2,5-disubstituted cyclohexenyl derivatives are utilized to generate the pendent ylide, then, A-phenylmaleimide is added in an intermolecular reaction, accessing highly substituted oxatricyclic derivatives such as 182 (Scheme 4.43). 

The typical primary vinylic substrate ( )-l-decenyl(phenyl)iodonium tetrafluor-oborate (11) displays unexpected reactivity under solvolytic conditions/ Its solvolysis was expected to be sluggish due to the instability of the possible primary vinyl cation intermediate, but it proceeded smoothly and as rapidly as that of the cyclohexenyl derivative 30 in alcoholic and aqueous solvents. However, the rates of solvolysis of 11 depend on the nucleophilicity of the solvent and not on the ionizing power. Both substitution (enol ether or aldehyde) and elimination products (19) are formed, in ratios which depend on the basicity of the medium (Scheme 46). 

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