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. 2012 Jul 16;51(29):7309-13.
doi: 10.1002/anie.201203382. Epub 2012 Jun 14.

Catalytic dynamic kinetic resolutions with N-heterocyclic carbenes: asymmetric synthesis of highly substituted β-lactones

Daniel T Cohen  1 , Chad C Eichman, Eric M Phillips, Emily R Zarefsky, Karl A Scheidt
Affiliations

Catalytic dynamic kinetic resolutions with N-heterocyclic carbenes: asymmetric synthesis of highly substituted β-lactones

Daniel T Cohen et al. Angew Chem Int Ed Engl. .

Erratum in

  • Angew Chem Int Ed Engl. 2013 May 10;52(20):5203

Abstract

New DKR type: An N-heterocyclic carbene (NHC)-catalyzed dynamic kinetic resolution of racemic α-substituted β-keto esters has been developed. This method relies on the epimerization of an NHC-enol intermediate before subsequent aldol/acylation events. Highly substituted β-lactones are produced in good yield with good to excellent selectivities (see scheme).

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Figures

Scheme 1
Scheme 1
NHC-Catalyzed Dynamic Kinetic Resolution
Scheme 2
Scheme 2
Parallel Kinetic Resolution
Scheme 3
Scheme 3
Synthetic Transformations[a]: [a] See supporting information for details. [b] PhCH2NH2, CH2Cl2, 23 °C. [c] SiO2, C6H6, 60°C. [d] LiAlH4, Et2O, 0 to 23 °C. [e] Ir(py)codPCy3, H2, CH2Cl2, 23°C. [f] ClSO2NH2, pyridine, CH2Cl2, 0 to 23 °C. [g] Rh2(OAc)4, MgO, PhI(OAc)2, CH2Cl2, 40 °C.
Scheme 4
Scheme 4
Proposed Reaction Pathway
See this image and copyright information in PMC

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