Thio-Claisen rearrangement used in preparing anti-β-functionalized γ,δ-unsaturated amino acids: Scope and limitations

Zhihua Liu, Sukeshi J. Mehta, Kwang Soo Lee, Bryan Grossman, Hongchang Qu, Xuyuan Gu, Gary S. Nichol, Victor J Hruby

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Abstract

Multifunctionalized amino acids, especially amino acids with unsaturation, are important, demanding building blocks in peptide chemistry. Here we present a summary of our most recent study using the thio-Claisen rearrangement for the synthesis of anti-β-functionalized γ,δ-unsaturated amino acids. Investigations on scope, limitations, chemoselectivities and stereoselectivities regarding an FeBr 3-catalyzed allylation strategy and a thio-enolate dianion formation strategy for asymmetric thio-Claisen rearrangement are documented. An explanation of the chirality crossover observed between the Eschenmoser-Claisen rearrangement and the thio-Claisen rearrangement is proposed. Novel optically active N α-protected amino acids with biologically interesting functional groups were prepared for the first time.

Original languageEnglish (US)
Pages (from-to)1289-1300
Number of pages12
JournalJournal of Organic Chemistry
Volume77
Issue number3
DOIs
Publication statusPublished - Feb 3 2012

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ASJC Scopus subject areas

  • Organic Chemistry

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