Fukuzumi and Bode
Supporting Information
Page S1
A Reagent for the Convenient, Solid Phase Synthesis of N-Terminal Peptide Hydroxylamines for
Chemoselective Ligations
Takeo Fukuzumi and Jeffrey W. Bode*
Roy and Diana Vagelos Laboratories, Department of Chemistry, University of Pennsylvania,
Philadelphia, PA 19104-6323, USA
Supporting Information
1. General Methods............................................................................................................................2
2. Preparation of Reagents..................................................................................................................3
3. Solution Phase Nitrone Synthesis and Conformation of Structure.................................................13
4. Solid-Phase Peptide Synthesis......................................................................................................15
5. General Procedure for Amine Oxidation Followed by Ligation on Solid Support .........................16
6. Control Reactions for Oxidations of N-Terminal Peptides Amines ...............................................17
7. Establishment of Stereorention at N-Terminus Following Oxidation ............................................19
8. Tentative Structure of Reaction Side Product and Effect of Reagent Stereochemistry...................20
9. Charactrization Data and HPLC Traces for Peptides.....................................................................23
Fukuzumi and Bode
Supporting Information
Page S2
1. General Methods
Reagents: All reactions utilizing air- or moisture-sensitive reagents were performed in dried glassware
under an atmosphere of dry Argon. CH2Cl2 was distilled over CaH2. THF was distilled from
Na/benzophenone. CH3OH and DMF were dried by passage over molecular sieves under Ar
atmosphere. N,N-Diisopropylethylamine (DIPEA) was distilled from CaH2. Other reagents were used
without further purification. Oxone was purchased from Alfa Aesar. Thin layer chromatogr