“…Deacylation of amide 10 by formation of the imino chloride and imidate and hydrolysis gave the corresponding primary amine. This was directly acylated using the acid chloride 6 and N -alkylated using the sulfonamide 11 to produce the target diene 3 . 2 Synthesis of Metathesis−Macrocyclization Precursor 3 …”
The synthesis of a range of highly functionalized peptidomimetic macrocycles has been accomplished using ring-closing metathesis and enyne tandem cross-metathesis-ring-closing metathesis reactions. This approach gives access to rigidified macrocycles modeled on the structures of cyclic peptides and designed to be biologically stable. The potential for peripheral functionalization of these templates has been demonstrated using Diels-Alder reactions, palladium(0) coupling reactions, and amide formation both in the solution phase and using polymer-supported syntheses.
“…3-Toluenesulfonyl-2-methylene-3-azabicyclo[3.1.0]hexane (39). Tosylamide 37 (100 mg, 0.47 mmol) was dissolved in 10 mL of THF and cooled to 0 °C. Lithium hexamethylsilylamide (0.50 mL of a 1 M solution in THF, 0.50 mmol) was added slowly and the reaction stirred 30 min at 0 °C before being brought to reflux.…”
The addition of simple pentadienyltosylamide derivatives to the two-carbon electrophile phenyl(propynyl)iodonium triflate initiates a sequence of transformations that furnishes complex, highly functionalized cyclopentenannelated dihydropyrrole products in moderate yields with complete stereoselection. This sequence demonstrates that diyls resulting from homolytic scission of alkylidene carbene-alkene adducts can be readily accessed under mild experimental conditions and that, in the presence of appropriate pendant functionality, these diyls can productively cyclize. The isomeric isoprene-derived tosylamides follow an abbreviated reaction course and deliver azabicyclo[3.1.0]hexanes via an isomerization that competes with diyl formation.
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