Complete Field Guide to Asymmetric BINOL-Phosphate Derived Brønsted Acid and Metal Catalysis: History and Classification by Mode of Activation; Brønsted Acidity, Hydrogen Bonding, Ion Pairing, and Metal Phosphates

Iron Catalysis in Organic Synthesis

Isatins As Privileged Molecules in Design and Synthesis of Spiro-Fused Cyclic Frameworks

Flow chemistry involves the use of channels or tubing to conduct a reaction in a continuous stream rather than in a flask Flow equipment provides chemists with unique control over reaction parameters enhancing reactivity or in some cases enabling new reactions This relatively young technology has received a remarkable amount of attention in the past decade with many reports on what can be done in flow Until recently, however, the question, “Should we do this in flow?” has merely been an afterthought This review introduces readers to the basic principles and fundamentals of flow chemistry and critically discusses recent flow chemistry accounts

The Hitchhiker's Guide to Flow Chemistry

The legacy of Gilbert Newton Lewis (1875-1946) pervades the lexicon of chemical bonding and reactivity. The power of his concept of donor-acceptor bonding is evident in the eponymous foundations of electron-pair acceptors (Lewis acids) and donors (Lewis bases). Lewis recognized that acids are not restricted to those substances that contain hydrogen (Bronsted acids), and helped overthrow the "modern cult of the proton". His discovery ushered in the use of Lewis acids as reagents and catalysts for organic reactions. However, in recent years, the recognition that Lewis bases can also serve in this capacity has grown enormously. Most importantly, it has become increasingly apparent that the behavior of Lewis bases as agents for promoting chemical reactions is not merely as an electronic complement of the cognate Lewis acids: in fact Lewis bases are capable of enhancing both the electrophilic and nucleophilic character of molecules to which they are bound. This diversity of behavior leads to a remarkable versatility for the catalysis of reactions by Lewis bases.

Lewis Base Catalysis in Organic Synthesis

Enantioselective diverse synthesis of a small-molecule collection with structural and functional similarities or differences in an efficient manner is an appealing but formidable challenge. Asymmet...

Diversified Transformations of Tetrahydroindolizines to Construct Chiral 3-Arylindolizines and Dicarbofunctionalized 1,5-Diketones.

Highly enantioselective Diels-Alder (DA) and inverse-electron-demand hetero-Diels-Alder (HDA) reactions of β,γ-unsaturated α-ketoesters with cyclopentadiene catalyzed by chiral N,N'-dioxide-Cu(OTf)(2) (Tf=triflate) complexes have been developed. Quantitative conversion of β,γ-unsaturated α-ketoesters and excellent diastereoselectivities (up to 99:1) and enantioselectivities (up to >99% ee) were observed for a broad range of substrates. Both aromatic and aliphatic β,γ-unsaturated α-ketoesters were found to be suitable substrates for the reactions. Moreover, the chemoselectivity of the DA and HDA adducts were improved by regulating the reaction temperature. Good to high chemoselectivity (up to 94%) of the DA adducts were obtained at room temperature, and moderate chemoselectivity (up to 65%) of the HDA adducts were achieved at low temperature. The reaction also featured mild reaction conditions, a simple procedure, and remarkably low catalyst loading (0.1-1.5 mol%). A strong positive nonlinear effect was observed.

Asymmetric Diels–Alder and Inverse‐Electron‐Demand Hetero‐Diels–Alder Reactions of β,γ‐Unsaturated α‐Ketoesters with Cyclopentadiene Catalyzed by N,N′‐Dioxide Copper(II) Complex

Determination of concentration and enantiomeric excess of amines and amino alcohols with a chiral nickel(II) complex.

A chiral thulium(III)-catalyzed sulfur-conjugation addition reaction of dialkynylphosphine oxides to construct P-stereogenic centers has been developed. Dialkynylphosphine oxides bearing aryl, alky...

Asymmetric Synthesis of P-Stereogenic Compounds via Thulium(III)-Catalyzed Desymmetrization of Dialkynylphosphine Oxides

Halofunctionalization methods enable the vicinal difunctionalization of alkenes with heteroatom nucleophiles and halogen moieties. As a fundamental transformation in organic synthesis, the catalytic asymmetric variants have only recently been reported. In sharp contrast to the asymmetric halocyclization of simple alkenes which involves a nucleophile-assisted alkene activation process, the asymmetric halofunctionalization of enones developed by our laboratory features an electrophile-assisted 1,4-addition pathway. Our work in this area has resulted in the development of several different types of regio-, diastereo-, and enantioselective processes, including inter- and intramolecular haloaminations, haloetherifications, and haloazidations. The scope, updated mechanism, limitations, and future perspective of these reactions are discussed.

Xiaohua Liu

Papers

Diversified Transformations of Tetrahydroindolizines to Construct Chiral 3-Arylindolizines and Dicarbofunctionalized 1,5-Diketones.

Asymmetric Diels–Alder and Inverse‐Electron‐Demand Hetero‐Diels–Alder Reactions of β,γ‐Unsaturated α‐Ketoesters with Cyclopentadiene Catalyzed by N,N′‐Dioxide Copper(II) Complex

Determination of concentration and enantiomeric excess of amines and amino alcohols with a chiral nickel(II) complex.

Asymmetric Synthesis of P-Stereogenic Compounds via Thulium(III)-Catalyzed Desymmetrization of Dialkynylphosphine Oxides

Asymmetric Catalytic Halofunctionalization of α,β-Unsaturated Carbonyl Compounds