Synthesis of 2,6-trans-tetrahydropyrans using a palladium-catalyzed oxidative heck redox-relay strategy

Bonfield, Holly E. and Edge, Colin M. and Reid, Marc and Kennedy, Alan R. and Pascoe, David D. and Lindsay, David M. and Valette, Damien (2024) Synthesis of 2,6-trans-tetrahydropyrans using a palladium-catalyzed oxidative heck redox-relay strategy. Organic Letters, 26 (14). pp. 2857-2861. ISSN 1523-7060 (https://doi.org/10.1021/acs.orglett.3c03866)

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Abstract

The C-aryl-tetrahydropyran motif is prevalent in nature in a number of natural products with biological activity; however, this challenging architecture still requires novel synthetic approaches. We demonstrate the application of a stereoselective Heck redox-relay strategy for the synthesis of functionalized 2,6-trans-tetrahydropyrans in excellent selectivity in a single step from an enantiopure dihydropyranyl alcohol, proceeding through a novel exo-cyclic migration. The strategy has also been applied to the total synthesis of a trans-epimer of the natural product centrolobine in excellent yield and stereoselectivity.

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