title: Regioselective solid-phase synthesis of N-mono-hydroxylated and N-mono-methylated acylpolyamine spider toxins using an 2-(ortho-nitrophenyl)ethanal-modified resin.
abstract: A recently introduced new SPS resin, possessing a 2-(ortho-nitrophenyl)ethanal linker, was used for the regioselective on-resin synthesis of N-mono-hydroxylated and N-mono-methylated polyamine spider toxins of Agelenopsis aperta and Larinioides folium. The polyamine backbones of the target compounds were efficiently constructed from the center by reductive amination of the aldehyde linker, followed by stepwise alkylation and acylation on solid support. Depending on the cleavage conditions, employing either oxidation/Cope elimination or methylation/Hofmann elimination, regioselectively the respective N-hydroxyl or N-methyl products were obtained. Employing this methodology, a number of acylpolyamine spider toxins were synthesized and identified as venom components by UHPLC and ESI-MS/MS.
authors.affiliation: Department of Chemistry, University of Zurich, Winterthurerstrasse 190, CH-8057 Zurich, Switzerland. stefan.bienz@chem.uzh.ch.
authors.forename: Denise
authors.initials: D
authors.lastname: Pauli
authors.forename: Stefan
authors.initials: S
authors.lastname: Bienz
mesh_terms: D000079:Acetaldehyde / Q000737:chemistry*; D000215:Acylation; D000818:Animals; D006900:Hydroxylation; D008745:Methylation; D011073:Polyamines / Q000138:chemical synthesis* / Q000737:chemistry; D060327:Solid-Phase Synthesis Techniques / Q000379:methods*; D013111:Spider Venoms / Q000138:chemical synthesis* / Q000737:chemistry; D013112:Spiders / Q000737:chemistry*
chemical_list: D011073:Polyamines; D013111:Spider Venoms; D000079:Acetaldehyde