Functionalized cyclopentenes through a tandem NHC-catalyzed dynamic kinetic resolution and ambient temperature decarboxylation: Mechanistic insight and synthetic application

Daniel T. Cohen; Ryne C. Johnston; Nicholas T. Rosson; Paul Ha Yeon Cheong; Karl A. Scheidt

doi:10.1039/c4cc09308a

Functionalized cyclopentenes through a tandem NHC-catalyzed dynamic kinetic resolution and ambient temperature decarboxylation: Mechanistic insight and synthetic application

Daniel T. Cohen, Ryne C. Johnston, Nicholas T. Rosson, Paul Ha Yeon Cheong^*, Karl A. Scheidt

^*Corresponding author for this work

Chemistry

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

24 Scopus citations

Abstract

An unusual room temperature β-lactone decarboxylation facilitated a five-step enantioselective formal synthesis of the cyclopentane core of an estrogen receptor β-agonist. A computational study probed the underlying factors facilitating unprecedented, rapid decarboxylation. Aryl substitution promotes faster reaction in the retro-[2+2] as a result of conjugative stabilization with the forming olefin. Additionally, the configuration of the α-ester in these fused β-lactones leads to differential decarboxylation rates.

Original language	English (US)
Pages (from-to)	2690-2693
Number of pages	4
Journal	Chemical Communications
Volume	51
Issue number	13
DOIs	https://doi.org/10.1039/c4cc09308a
State	Published - Feb 14 2015

ASJC Scopus subject areas

Electronic, Optical and Magnetic Materials
General Chemistry
Ceramics and Composites
Metals and Alloys
Materials Chemistry
Surfaces, Coatings and Films
Catalysis

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10.1039/c4cc09308a

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title = "Functionalized cyclopentenes through a tandem NHC-catalyzed dynamic kinetic resolution and ambient temperature decarboxylation: Mechanistic insight and synthetic application",

abstract = "An unusual room temperature β-lactone decarboxylation facilitated a five-step enantioselective formal synthesis of the cyclopentane core of an estrogen receptor β-agonist. A computational study probed the underlying factors facilitating unprecedented, rapid decarboxylation. Aryl substitution promotes faster reaction in the retro-[2+2] as a result of conjugative stabilization with the forming olefin. Additionally, the configuration of the α-ester in these fused β-lactones leads to differential decarboxylation rates.",

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Functionalized cyclopentenes through a tandem NHC-catalyzed dynamic kinetic resolution and ambient temperature decarboxylation: Mechanistic insight and synthetic application. / Cohen, Daniel T.; Johnston, Ryne C.; Rosson, Nicholas T. et al.
In: Chemical Communications, Vol. 51, No. 13, 14.02.2015, p. 2690-2693.

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

TY - JOUR

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AU - Cohen, Daniel T.

AU - Johnston, Ryne C.

AU - Rosson, Nicholas T.

AU - Cheong, Paul Ha Yeon

AU - Scheidt, Karl A.

PY - 2015/2/14

Y1 - 2015/2/14

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AB - An unusual room temperature β-lactone decarboxylation facilitated a five-step enantioselective formal synthesis of the cyclopentane core of an estrogen receptor β-agonist. A computational study probed the underlying factors facilitating unprecedented, rapid decarboxylation. Aryl substitution promotes faster reaction in the retro-[2+2] as a result of conjugative stabilization with the forming olefin. Additionally, the configuration of the α-ester in these fused β-lactones leads to differential decarboxylation rates.

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Functionalized cyclopentenes through a tandem NHC-catalyzed dynamic kinetic resolution and ambient temperature decarboxylation: Mechanistic insight and synthetic application

Abstract

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