TY - JOUR
T1 - The Cycloaddition of Vinylaziridines with Unsaturated Substrates
AU - Hassner, Alfred
AU - Chau, William
AU - D'Costa, Rosario
PY - 1982
Y1 - 1982
N2 - Vinylaziridines undergo ring expansion reactions which in case of divinylaziridines lead to dihydroazepines. Addition of 2‐phenyl‐2‐vinyl‐aziridine 10a to dimethyl acetylene dicarboxylate provides a facile method of in situ generation of a divinylaziridine and leads to isolation of an azepine derivative. Likewise we show that cycloaddition of 10a proceeds even with olefinic nitriles, sulfones and esters with formation of tetrahydroazepines. However, when the substrates are unsaturated nitro compounds or ketones, a novel rearrangement to open chain enamine derivatives takes place. Deuterium labelling in the β‐nitrostyrene substrate and in the vinylaziridine provide evidence for a retro‐ene reaction mechanism leading to the rearrangement. These data provide a framework for assessing the factors that guide the reactions either towards formation of seven‐membered ring azepine derivatives or toward open‐chain rearranged products.
AB - Vinylaziridines undergo ring expansion reactions which in case of divinylaziridines lead to dihydroazepines. Addition of 2‐phenyl‐2‐vinyl‐aziridine 10a to dimethyl acetylene dicarboxylate provides a facile method of in situ generation of a divinylaziridine and leads to isolation of an azepine derivative. Likewise we show that cycloaddition of 10a proceeds even with olefinic nitriles, sulfones and esters with formation of tetrahydroazepines. However, when the substrates are unsaturated nitro compounds or ketones, a novel rearrangement to open chain enamine derivatives takes place. Deuterium labelling in the β‐nitrostyrene substrate and in the vinylaziridine provide evidence for a retro‐ene reaction mechanism leading to the rearrangement. These data provide a framework for assessing the factors that guide the reactions either towards formation of seven‐membered ring azepine derivatives or toward open‐chain rearranged products.
UR - http://www.scopus.com/inward/record.url?scp=45249123461&partnerID=8YFLogxK
U2 - 10.1002/ijch.198200014
DO - 10.1002/ijch.198200014
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AN - SCOPUS:45249123461
SN - 0021-2148
VL - 22
SP - 76
EP - 81
JO - Israel Journal of Chemistry
JF - Israel Journal of Chemistry
IS - 1
ER -