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First Propargyl Azides Bearing Strong Acceptor Substituents and Their Effective Conversion into Allenyl Azides: Influence of the Electronic Effects of Substituents on the Reactivity of Propargyl Azides
Author(s) -
Fotsing Joseph Rodolph,
Banert Klaus
Publication year - 2005
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.200500135
Subject(s) - propargyl , chemistry , nucleophile , pyrazine , reactivity (psychology) , azide , medicinal chemistry , yield (engineering) , acceptor , organic chemistry , catalysis , medicine , materials science , alternative medicine , physics , pathology , metallurgy , condensed matter physics
Abstract We have succeeded in the synthesis of propargyl azides containing 1‐ or 3‐phenylthio functionalities. The selective oxidation of their sulfur atoms to sulfoxides and sulfones allows access to the first propargyl azides bearing acceptor substituents. Interestingly, the prototropic rearrangement of the latter propargyl azides leads to the formation of allenyl azides with relatively high stabilities and with moderate to good yields. Propargyl azides containing phenylthio functionalities react in the presence of nucleophiles to afford the expected N ‐unsubstituted 1,2,3‐triazoles via short‐lived allenyl azides. These results are entirely different from those of the corresponding sulfoxides and sulfones, which react under the analogous conditions either to produce the corresponding bis(triazolo)pyrazine derivatives or to yield newly substituted vinyl azides. The latter compounds can successfully be used as starting material providing access to azirines. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)