Abstract

A photoinduced Wolff rearrangement/chiral isothiourea catalyzed [4+2] cycloaddition reaction of pyrazolone derivatives and α‐diazoketones was developed, affording the corresponding dihydropyrano[2,3‐c]pyrazolone derivatives in moderate to good yields (50‐94%) with satisfactory to excellent diastereoselectivities (> 20:1 dr, in almost all cases) and enantioselectivities of 31‐99%. This protocol features readily available substrates, mild reaction conditions, and effective construction of vicinal tertiary and quaternary carbon stereocenters.

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