摘要：

The proximity effect in the Swern oxidation of cis,cis-1,3,5-tris(hydroxymethyl)-1,3,5-trimethylcyclohexane (Lf:) with TFAA was examined. The oxidation reaction of triol 4 with DMSO, TFAA, and relatively small amounts of triethylamine gave 5-formyl-cis,cis-1,3,5-trimethyl-3-hydroxymethyl-cyclohexane-1-carboxylic acid hemiacetal (7a) as well as 1,7,9-trimethyl-3,5,12-trioxawurtzitane (6), 5-formyl-cis,cis-1,3,5-trimethyl-3-hydroxymethylcyclohexane-1-carboxylic acid lactone (5), and polymers of cis,cis-1,3,5-triformyl-1,3,5-trimethylcyclohexane (2). Hemiacetal 7a underwent novel solvent-dependent conversions to hemiacetal 7b, lactone 5, or 1,7,9-trimethyl-2-oxo-3,5-dioxatricyclo-[5.3.1.0(4,9)]undecane (8) via 5-formyl-cis,cis-1,3,5-trimethyl-3-hydroxymethylcyclohexane-1-carboxylic acid. In the cases of relatively large amounts of triethylamine, trialdehyde 2 was given in moderate yield.

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