Novel aprotic polar solvents are selected for use towards a facile Baylis-Hillman reaction catalyzed by the standard base (DABCO) at room temperature so that less reactive aldehydes and a broad spectrum of activated olefins (including acrylamide) could be coupled under the altered reaction conditions.
An innovative synthetic protocol is reported for the ready access to 3‐deoxy sugars in both D and L forms as exclusive products (des >95 %) in high yields through a stereodefined Lewis acid catalyzed reaction sequence of the sugar‐derived Baylis–Hillman adducts.
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