A class of bifunctional phosphinothioureas derived from saccharide was developed as new organocatalysts for the enantioselective Morita‐Baylis‐Hillman reaction between acrylates and aldehydes. With 10 mol% of glucose‐based phosphinothiourea 1d, the allylic alcohols were obtained in up to 96% yield and 83% ee under mild reaction conditions.

The saccharide‐based chiral bifunctional thiourea‐phosphines were developed as chiral organocatalysts for the intramolecular Morita‐Baylis‐Hillman reaction of ω‐formyl‐enones. With only 2 mol% of thiourea‐phosphine catalyst 3c, chiral functionalized cyclohexenes were achieved under mild reaction conditions with excellent yields and enantioselectivities.

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