Pudovik addition/[1,2]-phospha-Brook rearrangement as an efficient tool for generation of anionic nucleophiles is an attractive strategy for the construction of C–C bonds in organic synthesis. Herein, we report organocatalytic 1,6-conjugate addition of para-quinone methides utilizing Pudovik addition/[1,2]-phospha-Brook rearrangement. Chiral guanidine–sulfonamide catalyzed the three-component reaction efficiently, providing biologically active oxindole/biaryl/phosphorus-based structures in high yields with excellent diastereo- and enantioselectivities. A possible bifunctional catalytic mode was proposed to elucidate the chiral control of this process.

An asymmetric three-component 1,3-dipolar cycloaddition of 3,4-dihydroisoquinolines, bromoacetates and α,β-unsaturated pyrazole amide is realized by using a chiral N,N'-dioxide-Y(OTf) 3 complex as the catalyst. The process includes a base-promoted formation of dihydroisoquinolium ylides in situ, and a chiral Lewis acid-catalyzed asymmetric [3 + 2] cycloaddition with α,β-unsaturated pyrazole amides. A series of hexahydropyrrolo-isoquinolines are obtained in moderate to good yields with excellent diastereo-and enantioselectivities.

A visible‐light‐induced acyl radical conjugate addition to electron‐deficient alkenes with acylsilane was realized by merging photoredox and Lewis acid catalysis under mild reaction conditions. Various tri‐ and tetra‐substituted furans were obtained with good yield (up to 97%) from α,β‐unsaturated ketones. Based on the experimental results and spectral analysis, a possible catalytic cycle involving 1,4‐conjugate addition/ring‐closure/arylation sequence was proposed. Beyond that, 1,6‐acyl radical conjugate addition to para‐quinone methides was also accomplished to deliver a series of α‐aryl ketones by using this synergistic catalysis protocol.

A visible-light-induced acyl radical conjugate addition to electron-deficient alkenes with acylsilane was realized by merging photoredox and Lewis acid catalysis under mild reaction conditions. Various tri- and tetra-substituted furans were obtained with good yield (up to 97%) from α,β-unsaturated ketones. Based on the experimental results and spectral analysis, a possible catalytic cycle involving 1,4-conjugate addition/ring-closure/arylation sequence was proposed. Beyond that, 1,6-acyl radical conjugate addition to para-quinone methides was also accomplished to deliver a series of α-aryl ketones by using this synergistic catalysis protocol.