1009093-14-4Relevant articles and documents
Synthetic Studies Toward the Skyllamycins: Total Synthesis and Generation of Simplified Analogues
Giltrap, Andrew M.,Haeckl, F. P. Jake,Kurita, Kenji L.,Linington, Roger G.,Payne, Richard J.
, p. 7250 - 7270 (2018/06/01)
Herein, we report our synthetic studies toward the skyllamycins, a highly modified class of nonribosomal peptide natural products which contain a number of interesting structural features, including the extremely rare α-OH-glycine residue. Before embarking on the synthesis of the natural products, we prepared four structurally simpler analogues. Access to both the analogues and the natural products first required the synthesis of a number of nonproteinogenic amino acids, including three β-OH amino acids that were accessed from the convenient chiral precursor Garner's aldehyde. Following the preparation of the suitably protected nonproteinogenic amino acids, the skyllamycin analogues were assembled using a solid-phase synthetic route followed by a final stage solution-phase cyclization reaction. To access the natural products (skyllamycins A-C) the synthetic route used for the analogues was modified. Specifically, linear peptide precursors containing a C-terminal amide were synthesized via solid-phase peptide synthesis. After cleavage from the resin the N-terminal serine residue was oxidatively cleaved to a glyoxyamide moiety. The target natural products, skyllamycins A-C, were successfully prepared via a final step cyclization with concomitant formation of the unusual α-OH-glycine residue. Purification and spectroscopic comparison to the authentic isolated material confirmed the identity of the synthetic natural products.
Iron(II)-catalyzed intramolecular aminohydroxylation of olefins with functionalized hydroxylamines
Liu, Guan-Sai,Zhang, Yong-Qiang,Yuan, Yong-An,Xu, Hao
supporting information, p. 3343 - 3346 (2013/04/23)
A diastereoselective aminohydroxylation of olefins with a functionalized hydroxylamine is catalyzed by new iron(II) complexes. This efficient intramolecular process readily affords synthetically useful amino alcohols with excellent selectivity (dr up to > 20:1). Asymmetric catalysis with chiral iron(II) complexes and preliminary mechanistic studies reveal an iron nitrenoid is a possible intermediate that can undergo either aminohydroxylation or aziridination, and the selectivity can be controlled by careful selection of counteranion/ligand combinations.
Synthesis of a fluorine-substituted puromycin derivative for Bronsted studies of ribosomal-catalyzed peptide bond formation
Okuda, Kensuke,Hirota, Takashi,Kingery, David A.,Nagasawa, Hideko
experimental part, p. 2609 - 2612 (2009/07/18)
The mechanism by which the ribosome catalyzes peptide bond formation remains controversial. Here we describe the synthesis of a nucleoside that can be used in Bronsted experiments to assess the transition state of ribosome catalyzed peptide bond formation. This substrate is the nucleoside 3 -amino-3 -deoxy-3 -[(3 R)-3-fluoro-L-phenyl-alanyl]-N6,N 6-dimethyladenosine, which was prepared from (1R,2R)-2-amino-1- phenylpropane-1,3-diol. This substrate is active in peptide bond formation on the ribosome and is a useful probe for Bronsted analysis experiments on the ribosome.
