The cooperation and interplay between organic and metal catalyst systems is of utmost importance in nature and chemical synthesis. Here innovative and selective cooperative catalyst systems can be designed by combining two catalysts that complement rather than inhibit one another. This refined strategy can permit chemical transformations unmanageable by either of the catalysts alone. This review summarizes innovations and developments in selective organic synthesis that have used cooperative dual catalysis by combining simple aminocatalysts with metal catalysts. Considerable efforts have been devoted to this fruitful field. This emerging area employs the different activation modes of amine and metal catalysts as a platform to address challenging reactions. Here, aminocatalysis (e.g., enamine activation catalysis, iminium activation catalysis, single occupied molecular orbital (SOMO) activation catalysis, and photoredox activation catalysis) is employed to activate unreactive carbonyl substrates. The trans...

Combinations of Aminocatalysts and Metal Catalysts: A Powerful Cooperative Approach in Selective Organic Synthesis.

In recent years, visible light-driven organic photochemical synthesis has attracted wide research interest from academic and industrial communities due to its features of green and sustainable chemistry. In this flourishing area, Chinese chemists have devoted great efforts to different aspects of synthetic chemistry. This review will summarize their representative work according to the following categories: C–H functionalization, synthesis of aromatic aza-heterocycles, asymmetric organic photochemical synthesis, transformations of small molecules and biomolecule-compatible reactions.

Visible light-driven organic photochemical synthesis in China

Recent advances in the catalytic asymmetric 1,3-dipolar cycloaddition of azomethine ylides

Carbo- and heterocycles are widely found in natural products, biologically active structures, medicinally relevant compounds, and in many other fine chemicals. The development of novel, general and efficient methods for their construction has therefore gained great interest in synthetic organic chemistry. Recently, radical chemistry has become a heavily investigated research field (a renaissance!). Along these lines, radical cascade cyclization of 1,n-enynes and diynes has emerged as a powerful strategy for the preparation of carbo- and heterocycles. In this review, we highlight recent advances in this rapidly growing area also focusing on reaction mechanisms.

Radical cascade cyclization of 1,n-enynes and diynes for the synthesis of carbocycles and heterocycles

The selective functionalization of remote C–H bonds via intramolecular hydrogen atom transfer (HAT) is transformative for organic synthesis This radical-mediated strategy provides access to novel reactivity that is complementary to closed-shell pathways As modern methods for mild generation of radicals are continually developed, inherent selectivity paradigms of HAT mechanisms offer unparalleled opportunities for developing new strategies for C–H functionalization This review outlines the history, recent advances, and mechanistic underpinnings of intramolecular HAT as a guide to addressing ongoing challenges in this arena 1 	Introduction 2 	Nitrogen-Centered Radicals 21 	sp 3 N-Radical Initiation 22 	sp 2 N-Radical Initiation 3 	Oxygen-Centered Radicals 31 	Carbonyl Diradical Initiation 32 	Alkoxy Radical Initiation 33 	Non-alkoxy Radical Initiation 4 	Carbon-Centered Radicals 41 	sp 2 C-Radical Initiation 42 	sp 3 C-Radical Initiation 5 	Conclusion

Remote C-H Functionalization via Selective Hydrogen Atom Transfer.

Synthesis of Fused Pyran Derivatives via Visible-Light-Induced Cascade Cyclization of 1,7-Enynes with Acyl Chlorides.

Intramolecular 1,5-H transfer reaction of aryl iodides through visible-light photoredox catalysis: a concise method for the synthesis of natural product scaffolds

Herein we describe a mild method for the dual C(sp3 )-H bond functionalization of saturated nitrogen-containing heterocycles through a sequential visible-light photocatalyzed dehydrogenation/[2+2] cycloaddition procedure. As a complementary approach to the well-established use of iminium ion and α-amino radical intermediates, the elusive cyclic enamine intermediates were effectively generated by photoredox catalysis under mild conditions and efficiently captured by acetylene esters to form a wide array of bicyclic amino acid derivatives, thus enabling the simultaneous functionalization of two vicinal C(sp3 )-H bonds.

Dual C(sp 3 )-H Bond Functionalization of N-Heterocycles through Sequential Visible-Light Photocatalyzed Dehydrogenation/[2+2] Cycloaddition Reactions.

An efficient strategy for the synthesis of polysubstituted chromeno[4,3-b]pyrrolidine derivatives.

Dual C–H functionalization of N-aryl tetrahydroisoquinolines: a highly diastereoselective synthesis of dibenzo[a,f]quinolizines via visible-light induced oxidation and inverse electron-demand aza-Diels–Alder reaction

Guo-Qiang Xu

Papers

Synthesis of Fused Pyran Derivatives via Visible-Light-Induced Cascade Cyclization of 1,7-Enynes with Acyl Chlorides.

Intramolecular 1,5-H transfer reaction of aryl iodides through visible-light photoredox catalysis: a concise method for the synthesis of natural product scaffolds

Dual C(sp 3 )-H Bond Functionalization of N-Heterocycles through Sequential Visible-Light Photocatalyzed Dehydrogenation/[2+2] Cycloaddition Reactions.

An efficient strategy for the synthesis of polysubstituted chromeno[4,3-b]pyrrolidine derivatives.

Dual C–H functionalization of N-aryl tetrahydroisoquinolines: a highly diastereoselective synthesis of dibenzo[a,f]quinolizines via visible-light induced oxidation and inverse electron-demand aza-Diels–Alder reaction