Details

Autor(en) / Beteiligte

• Jin, You‐Xiang
• Yu, Bang‐Kui
• Qin, Si‐Ping
• Tian, Shi‐Kai

Titel

Epoxide‐Mediated Stevens Rearrangements of α‐Amino‐Acid‐Derived Tertiary Allylic, Propargylic, and Benzylic Amines: Convenient Access to Polysubstituted Morpholin‐2‐ones

Ist Teil von

• Chemistry : a European journal, 2019-04, Vol.25 (20), p.5169-5172

Ort / Verlag

Germany: Wiley Subscription Services, Inc

Erscheinungsjahr

2019

Quelle

Wiley Online Library Journals Frontfile Complete

Beschreibungen/Notizen

• A new strategy has been established for the synthesis of polysubstituted morpholin‐2‐ones through Stevens rearrangements of tertiary amines via in situ activation with epoxides. A range of α‐amino acid‐derived tertiary allylic, propargylic, and benzylic amines reacted with epoxides in the presence of zinc halide catalysts to afford structurally diverse allyl‐, allenyl‐, and benzyl‐substituted morpholin‐2‐ones, respectively, in moderate‐to‐good yields with high regioselectivity. The process involves [2,3]‐ and [1,2]‐Stevens rearrangements of quaternary ammonium ylide intermediates and constitutes a very convenient method to prepare polysubstituted morpholin‐2‐ones through tandem formation of C−N, C−O, and C−C bonds. Moreover, replacing epoxides with aziridines permitted the synthesis of polysubstituted piperazin‐2‐ones. New Stevens rearrangement: Zinc‐halide‐catalyzed ring‐opening of epoxides with α‐amino acid‐derived tertiary allylic, propargylic, and benzylic amines followed by [2,3]‐ and [1,2]‐Stevens rearrangements of the resulting quaternary ammonium ylide intermediates has been established as a convenient method to access polysubstituted morpholin‐2‐ones through tandem formation of C−N, C−O, and C−C bonds (see scheme).