Lithium Perchlorate Catalyzed Regioselective Ring Opening of Aziridines with Sodium Azide and Sodium Cyanide

Abstract

Aziridines react smoothly with sodium azide and sodium cyanide in the presence of catalytic amount of lithium perchlorate under essentially mild and neutral reaction conditions to afford the corresponding b-azido and b-cyanoamines in high yields with high regioselectivity.

Three‐Membered Heterocycles. Structure and Reactivity

“…To achieve virtually neutral conditions, trimethylsilyl azide can be used as the source of azide (Table 2.13, entry 1), along with catalytic amounts of tributylammonium fluoride (TBAF) to liberate the azide in situ [152]. Of course, sodium azide itself can be used as a reactant, with the addition being promoted efficiently by cerium trichloride heptahydrate [168], lithium perchlorate [169] or Oxone [170] (Scheme 2.25). Meso aziridines can be enantioselectively desymmetrized using a dimeric salen yttrium catalyst in near quantitative yield and excellent enantioselectivity [161].…”

Perchloric Acid and Its Salts: Very Powerful Catalysts in Organic Chemistry

“…261 The same catalytic system (10 mol % LiClO 4 in acetonitrile) is then used for ring-opening of aziridines with many nucleophiles. In this manner, β-amino-sulfides from thiols, β-azido-amines from sodium azide or β-cyano-amines from sodium cyanide are obtained in 82-93%, 262 85-92%, 263 and 80-87% 263 yields, respectively, at reflux temperature. 1,2-Diamines from aromatic amines and β-amino-thiocyanates from potassium thiocyanate are obtained in 83-95% 264 and 75-86% yield, 265 respectively, at room temperature as well.…”

Base-Controlled Diastereoselective Synthesis of Either anti- or syn-β-Aminonitriles

“…Routes to the β-aminonitrile functional group include ring opening of aziridines with cyanide, conjugate addition of amines to acrylonitriles, hydrocyanation of nitroalkenes, and Thorpe–Ziegler reaction between two nitriles followed by conjugate reduction . The most efficient method, and that which has led to many enantioselective syntheses through asymmetric transition metal catalysis, is the addition of alkanenitriles to imines .…”