title: Synthesis of Amathaspiramides by Aminocyanation of Enoates.
abstract: Concise routes for the total and formal syntheses of the amathaspiramides were developed through a formal [3+2] cycloaddition between lithium(trimethylsilyl)diazomethane and α,β-unsaturated esters. The effectiveness of this new cycloaddition for the construction of Δ(2)-pyrazolines containing a α-tert-alkylamino carbon center and subsequent facile protonolytic N-N bond cleavage allows the synthesis of a key intermediate of the amathaspiramides and other α,α-disubstituted amino acid derivatives.
authors.affiliation: Department of Chemistry, University of Illinois at Chicago, 845 West Taylor Street, Chicago, IL (USA).
authors.forename: Matthew
authors.initials: M
authors.lastname: O'Connor
authors.affiliation: Merck Discovery Chemistry, 2000 Galloping Hill Road, Kenilworth, NJ 07033 (USA).
authors.forename: Chunrui
authors.initials: C
authors.lastname: Sun
authors.affiliation: Department of Chemistry, University of Illinois at Chicago, 845 West Taylor Street, Chicago, IL (USA). dsunglee@uic.edu.
authors.forename: Daesung
authors.initials: D
authors.lastname: Lee
mesh_terms: D003500:Cyclization; D003978:Diazomethane / Q000031:analogs & derivatives / Q000737:chemistry*; D004952:Esters / Q000737:chemistry*; D008094:Lithium / Q000737:chemistry*; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000737:chemistry*; D011720:Pyrazoles / Q000138:chemical synthesis* / Q000737:chemistry; D013141:Spiro Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism; D014297:Trimethylsilyl Compounds / Q000737:chemistry*
chemical_list: D004952:Esters; D009942:Organometallic Compounds; D011720:Pyrazoles; D013141:Spiro Compounds; D014297:Trimethylsilyl Compounds; C000607211:amathaspiramide C; D003978:Diazomethane; D008094:Lithium
keywords: amino acid; cycloaddition; diazo compounds; natural products; total synthesis