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Tandem palladium and isothiourea relay catalysis: enantioselective synthesis of α-amino acid derivatives via allylic amination and [2,3]-sigmatropic rearrangement

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Author(s)

Stephanie S. M. Spoehrle, Thomas H. West, James E. Taylor, Alexandra M. Z. Slawin, Andrew D. Smith

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Abstract

A tandem relay catalytic protocol using both Pd and isothiourea catalysis has been developed for the enantioselective synthesis of α-amino acid derivatives containing two stereogenic centers from readily accessible N,N-disubstituted glycine aryl esters and allylic phosphates. The optimized process uses a bench-stable succinimide-based Pd precatalyst (FurCat) to promote Pd-catalyzed allylic ammonium salt generation from the allylic phosphate and the glycine aryl ester. Subsequent in situ enantioselective [2,3]-sigmatropic rearrangement catalyzed by the isothiourea benzotetramisole forms syn-α-amino acid derivatives with high diastereo- and enantioselectivity. This methodology is most effective using 4-nitrophenylglycine esters and tolerates a variety of substituted cinnamic and styrenyl allylic ethyl phosphates. The use of challenging unsymmetrical N-allyl-N-methylglycine esters is also tolerated under the catalytic relay conditions without compromising stereoselectivity.
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Original languageEnglish
Pages (from-to)11895-11902
Number of pages8
JournalJournal of the American Chemical Society
Volume139
Issue number34
Early online date1 Aug 2017
DOIs
Publication statusPublished - 30 Aug 2017

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