%0 Journal Article %A Liu, Zhihua %A Mehta, Sukeshi J. %A Lee, Kwang-Soo %A Grossman, Bryan %A Qu, Hongchang %A Gu, Xuyuan %A Nichol, Gary S. %A Hruby, Victor J. %D 2016 %T Thio-Claisen Rearrangement Used in Preparing Anti-β-Functionalized γ,δ-Unsaturated Amino Acids: Scope and Limitations %U https://acs.figshare.com/articles/journal_contribution/Thio_Claisen_Rearrangement_Used_in_Preparing_Anti_Functionalized_Unsaturated_Amino_Acids_Scope_and_Limitations/2553421 %R 10.1021/jo201753q.s002 %2 https://acs.figshare.com/ndownloader/files/4196479 %K building blocks %K chirality crossover %K acid %K strategy %K peptide chemistry %K rearrangement %X 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 FeBr3-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 Nα-protected amino acids with biologically interesting functional groups were prepared for the first time. %I ACS Publications