In recent years, the catalytic enantioselective reactions of p-QMs have drawn much attention, because of their distinctive reactivities. As such, a variety of chiral catalytic systems have been developed. This Focus Review describes the reactions of p-QMs according to the chiral catalyst system used, with the aim of provide the first complete picture of the exciting developments in this field. Special emphasis is placed on recent work regarding their reaction mechanisms.

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The first enantioselective cycloaddition of ortho‐hydroxyphenyl substituted para‐quinone methides has been established by employing isatin‐derived enals as suitable 3C‐synthons under chiral N‐heterocyclic carbene catalysis. By using this strategy, biologically important ϵ‐lactones have been prepared in good yields (up to 89%) and excellent asymmetric inductions (up to >99% ee, >20:1 dr). Notably, this methodology opens a direct [4+3] annulation entry for the asymmetric synthesis of spirobenzoxopinones bearing an oxindole moiety connected through the spirocenter.magnified image

Chiral cyclohex-2-enones are important building blocks in synthetic chemistry and the life science industries and much attention has been drawn to the development of efficient and practical methodologies for accessing these enantio-enriched cyclohex-2-enone skeletons. This review describes the impressive progress that has been made in terms of employing new methodologies, suitable reactants as well as more efficient catalyst systems for this important enantioselective transformation. Also, the reaction mechanisms are briefly discussed.

A remote stereocontrolled 1,8-conjugate addition of thiazolones to propargylic aza-p-quinone methides formed from propargylic alcohols has been developed with the aid of a chiral phosphoric acid, and this represents the first report on organocatalytic stereocontrolled 1,8-addition of propargylic aza-p-quinone methides. Notably, the remote stereocontrolled activation protocol enables the construction of vicinal sulfur-containing quaternary carbon stereocenters and axially chiral tetrasubstituted allenes and promotes the chemistry of chiral phosphoric acids.