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First [4+2] Cycloadditions Involving the Olefinic Bond of an ‘Aldoketeniminium Salt’ (=N-Alk-1-enylideneaminium Salt)

✍ Scribed by Florence Mahuteau-Betzer; Ping-Yu Ding; Léon Ghosez


Publisher
John Wiley and Sons
Year
2005
Tongue
German
Weight
227 KB
Volume
88
Category
Article
ISSN
0018-019X

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✦ Synopsis


Abstract

‘Keteniminium triflates’ (=N‐alk‐1‐enylideneaminium trifluoromethanesulfonates; [MeN(Ts)CHC NR^1^(R^2^)]^+^TfO^−^) generated in situ from N^α^‐tosylsarcosinamides MeN(Ts)CH~2~CONR^1^(R^2^) unexpectedly react with cyclopenta‐1,3‐diene and cyclohexa‐1,3‐diene to give Diels–Alder reactions across the CC bond of the cumulene. The use of N^α^‐tosylsarcosinamides derived from chiral pyrrolidines allows the direct preparation of trinorbornenone derivative 6 in high enantiomer purity.