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
10.1021/jo201753q.s002
https://acs.figshare.com/articles/journal_contribution/Thio_Claisen_Rearrangement_Used_in_Preparing_Anti_Functionalized_Unsaturated_Amino_Acids_Scope_and_Limitations/2553421
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<sub>3</sub>-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 <i>N</i><sup>α</sup>-protected amino acids with biologically
interesting functional groups were prepared for the first time.
2016-02-22 06:58:03
building blocks
chirality crossover
acid
strategy
peptide chemistry
rearrangement