Total Synthesis of (-)-Reveromycin A via a Hetero-Diels-Alder Approach

Reported here are details on the discovery of a phosphine-catalyzed isomerization of hemiketals and subsequent reactions of the cyclic keto enol ether products. The new cycloisomerization complements a previously reported amine-catalyzed process that gave oxepinones from the same hemiketal starting materials. In the absence of functionality (R(2)) on the cyclic keto enol ether, a rapid and facile dimerization occurs, giving spiroketal products. When the enone is substituted (i.e., R(2) = Ph), the cyclic keto enol ether is sufficiently stable so that it can be isolated; it can then be further reacted in the same pot to provide the corresponding dihydropyrazoles. Both the spiroketal and dihydropyrazole products arise by a tandem reaction that begins with the novel cycloisomerization. The method allows for the rapid introduction of complexity in the products from relatively simple starting materials. It should find application in the synthesis of natural product-like molecules.

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Applications of the Dess-Martin Oxidation in Total Synthesis of Natural Products

Heravi

Momeni

Zadsirjan

et al. 2021

COS

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: Dess–Martin periodinane (DMP), is a commercially available chemical, frequently being utilized as a mild oxidative agent for the selective oxidation of primary and secondary alcohols to their corresponding aldehydes and ketones, respectively. DMP shows several merits over other common oxidative agent such as chromium- and DMSO-based oxidants, thus it is habitually employed in the total synthesis of natural products. In this review, we try to underscore the applications of DMP as an effective oxidant in an appropriate step (steps) in the multistep total synthesis of natural products.

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Total Synthesis of (-)-Reveromycin A via a Hetero-Diels-Alder Approach

Cited by 3 publications

References 9 publications

Synthesis of 5,6- and 6,6-Spirocyclic Compounds

Synthesis of 5,6- and 6,6-Spirocyclic Compounds

Discovery of a Phosphine-Mediated Cycloisomerization of Alkynyl Hemiketals: Access to Spiroketals and Dihydropyrazoles via Tandem Reactions

Applications of the Dess-Martin Oxidation in Total Synthesis of Natural Products

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