Abstract

Stereoselective synthesis of a series of 1,3-dioxan-4-ylmethanes 1−9 has been achieved by use of solely substrate-based asymmetric induction. The simple C2-symmetric bis(dioxanyl)methane 1 has a greater than 99% conformational preference at the two inter-ring bonds for the conformation 1a. The homologous structures 3−9 contain up to five dioxanylmethane units, maintaining a high conformational preference in each of the bis(dioxanyl)methane units. Thus, these flexible compounds reach a conformational preference in excess of 90% over up to eight rotatable inter-ring bonds. (© Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)

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