%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