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Development of (Trimethylsilyl)ethyl Ester Protected Enolates and Applications in Palladium-Catalyzed Enantioselective Allylic Alkylation: Intermolecular Cross-Coupling of Functionalized Electrophiles

Corey M. Reeves, Douglas C. Behenna and Brian M. Stoltz*

*Division of Chemistry and Chemical Engineering, California Institute of Technology, 1200 East California Boulevard, MC 101-20, Pasadena, California 91125, United States, Email:

C. M. Reeves, D. C. Behenna, B. M. Stoltz, Org. Lett., 2014, 16, 2314-2317.

DOI: 10.1021/ol500355z

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The application of (trimethylsilyl)ethyl ester protected enolates in palladium-catalyzed asymmetric allylic alkylation provides a variety of α-quaternary six- and seven-membered ketones and lactams. The use of (trimethylsilyl)ethyl ester protected enolates offers enhanced allyl substrate scope relative to traditional β-ketoester substrates and is suitable for complex fragment coupling.

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Deracemization of Quaternary Stereocenters by Pd-Catalyzed Enantioconvergent Decarboxylative Allylation of Racemic β-Ketoesters

J. T. Mohr, D. C. Behenna, A. M. Harned, B. M. Stoltz, Angew. Chem. Int. Ed., 2005, 44, 6924-6927.

Catalytic Enantioselective Decarboxylative Protonation

J. T. Mohr, T. Nishimata, D. C. Behenna, B. M. Stoltz, J. Am. Chem. Soc., 2006, 128, 11348-11349.

Key Words

Tsuji-Trost Reaction, Cyclohexanones

ID: J54-Y2014