Thio-Claisen Rearrangement Used in Preparing Anti-β-Functionalized γ,δ-Unsaturated Amino Acids: Scope and Limitations

Autor:	Xuyuan Gu, Sukeshi J. Mehta, Bryan Grossman, Gary S. Nichol, Victor J. Hruby, Hongchang Qu, Zhihua Liu, Kwang Soo Lee
Rok vydání:	2012
Předmět:	Bromides Models Molecular chemistry.chemical_classification Degree of unsaturation Chemistry Stereochemistry Organic Chemistry Molecular Conformation Thio Stereoisomerism Optically active Catalysis Amino acid Claisen rearrangement Peptide chemistry Amino Acids Chirality (chemistry) Sulfur
Zdroj:	The Journal of Organic Chemistry. 77:1289-1300
ISSN:	1520-6904 0022-3263
DOI:	10.1021/jo201753q
Popis:	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.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_dedup___::ce6a5bb1ddc55fdcee9f271cab683204 https://doi.org/10.1021/jo201753q Zobrazit plný text záznamu