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Solutions of aza-Morita–Baylis–Hillman (aza-MBH) reactions were directly monitored by ESI(+)-MS(/MS) spectrometry to obtain information on their mechanism. A unique bis-sulfonamide intermediate was intercepted and characterized and, based on this novel species, a mechanism that rationalizes the uniqueness of aza-MBH reactions is proposed.

Graphical abstract: On the mechanism of the aza-Morita–Baylis–Hillman reaction: ESI-MS interception of a unique new intermediate

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