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Rearrangement of Hydroxylated Pinene Derivatives to Fenchone-Type Frameworks: Computational Evidence for Dynamically-Controlled Selectivity

Marcus Blümel, Shota Nagasawa, Katherine Blackford, Stephanie R Hare, Dean J Tantillo, Richmond Sarpong

J Am Chem Soc. 2018 Jul 25;140(29):9291-9298.

PMID: 29968475

Abstract:

An acid-catalyzed Prins/semipinacol rearrangement cascade reaction of hydroxylated pinene derivatives that leads to tricyclic fenchone-type scaffolds in very high yields and diastereoselectivity has been developed. Quantum chemical analysis of the selectivity-determining step provides support for the existence of an extremely flat potential energy surface around the transition state structure. This transition state structure appears to be ambimodal, i.e., the fenchone-type tricyclic scaffolds are formed in preference to the competing formation of a bornyl (camphor-type) skeleton under dynamic control via a post-transition state bifurcation (PTSB).

Chemicals Related in the Paper:

Catalog Number Product Name Structure CAS Number Price
AP4695629 (+)-Fenchone (+)-Fenchone 4695-62-9 Price
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