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

doi:10.1021/jacs.8b05804

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

Research output: Contribution to journal › Article › peer-review

13 Citations (Scopus)

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).

Original language	English
Pages (from-to)	9291-9298
Number of pages	8
Journal	Journal of the American Chemical Society
Volume	140
Issue number	29
DOIs	https://doi.org/10.1021/jacs.8b05804
Publication status	Published - 2018 Jul 25
Externally published	Yes

ASJC Scopus subject areas

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

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10.1021/jacs.8b05804

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

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).",

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AU - Nagasawa, Shota

AU - Blackford, Katherine

AU - Hare, Stephanie R.

AU - Tantillo, Dean J.

AU - Sarpong, Richmond

N1 - Funding Information: This work was supported by the National Science Foundation (NSF, CHE-1566430 to R.S. and CHE-1565933 and CHE-030089 [computational support via XSEDE] to D.T.). Publisher Copyright: © 2018 American Chemical Society.

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

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ASJC Scopus subject areas

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