Cyclopropanation of 1,3-dienes with ethyl 2-formyldiazoacetate under rhodium catalysis results in either a tandem cyclopropanation/Cloke−Wilson rearrangement or a vinylogous variant, depending on the diene used. These adducts may be subjected to an oxygen to nitrogen substitution with various amines under palladium catalysis. The substrate scope and mechanistic reasoning is presented.

Piotrowski, Mattew L.; Dekruyf, Daryyl SR; and Pagenkopf, Brian, "Oxidative cyclization of tertiary pentenol derivatives forming 2,5,5-trisubstituted THF rings and the total synthesis of cyclocapitelline" (2015). Chemistry Publications. 34.

The total synthesis of kainoid alkaloid, (+/–)‐β‐allokainic acid is reported. The key step is a vinylogous Cloke–Wilson rearrangement followed by Lewis acid and transition metal induced transformations to prepare a highly functionalized pyrrolidine suitable for conversion to the target molecule.

Oxidative Cyclization of Tertiary Pentenol Derivatives Forming 2,5,5-Trisubstituted THF Rings and the Total Synthesis of Cyclocapitelline. -A modified Mukaiyama oxidative cyclization of homoallylic alcohols under aerobic conditions is developed using a pre-oxidized cobalt complex as catalyst. The method provides access to trisubstituted tetrahydrofurans including the derivative (IIj), an intermediate in the synthesis of cyclocapitelline. -(PHILLIPS, G. A.; PALMER, C.; STEVENS, A. C.; PIOTROWSKI, M. L.; DEKRUYF, D. S. R.; PAGENKOPF*, B. L.; Tetrahedron Lett. 56 (2015) 44, 6052-6055, http://dx.

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