jo201753q_si_002.pdf (5.32 MB)
Thio-Claisen Rearrangement Used in Preparing Anti-β-Functionalized γ,δ-Unsaturated Amino Acids: Scope and Limitations
journal contribution
posted on 2016-02-22, 06:58 authored by Zhihua Liu, Sukeshi
J. Mehta, Kwang-Soo Lee, Bryan Grossman, Hongchang Qu, Xuyuan Gu, Gary S. Nichol, Victor J. HrubyMultifunctionalized 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.