Catalytic Allylation Of Aldehydes Research Articles

Recent Progress in Chromium-Mediated Carbonyl Addition Reactions

AbstractOrganochromium(III) species are versatile nucleophiles in complex molecule synthesis due to their high functional group tolerance and chemoselectivity for aldehydes. Traditionally, carbonyl addition reactions of organochromium(III) species were performed through reduction of organohalides either using stoichiometric chromium(II) salts or catalytic chromium salts in the presence of stoichiometric reductants [such as Mn(0)]. Recently, alternative methods emerged involving organoradical formation from readily available starting materials (e.g., N-hydroxyphthalimide esters, alkenes, and alkanes), followed by trapping the radical with stoichiometric or catalytic chromium(II) salts. Such methods, especially using catalytic chromium(II) salts, will lead to the development of sustainable chemical processes minimizing salt wastes and number of synthetic steps. In this review, methods for generation of organochromium(III) species for addition reactions to carbonyl compounds, classified by nucleophiles are described.1 Introduction2 Alkylation2.1 Branch-Selective Reductive Alkylation of Aldehydes Using Unactivated Alkenes2.2 Linear-Selective Alkylation of Aldehydes2.2.1 Catalytic Decarboxylative Alkylation of Aldehydes Using NHPI ­Esters2.2.2 Catalytic Reductive Alkylation of Aldehydes Using Unactivated Alkenes2.2.3 Alkylation of Aldehydes via C(sp3)–H Bond Functionalization of Unactivated Alkanes2.3 Catalytic α-Aminoalkylation of Carbonyl Compounds3 Allylation3.1 Catalytic Allylation of Aldehydes via Three-Component Coupling3.2 Catalytic Allylation of Aldehydes via C(sp3)–H Bond Functionalization of Alkenes4 Propargylation: Catalytic Propargylation of Aldehydes via Three-Component Coupling5 Conclusion

ChemInform Abstract: Catalytic Allylation of Aldehydes with Allyltrimethylsilane Using in situ Generated Trimethylsilyl Methanesulfonate (TMSOMs) as a Catalyst.

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Catalytic, Nucleophilic Allylation of Aldehydes with Allyl Acetate

A new catalytic allylation of aldehydes has been developed that employs allyl acetate as the allylating reagent. Under catalysis by ruthenium trichloride (3 mol %) in the presence of carbon monoxide (30 psi), water (1.5 equiv), and triethylamine (0.1 equiv), a wide range of aromatic, olefinic, and aliphatic aldehydes are efficiently allylated under mild conditions (70 degrees C, 24-48 h). The stoichiometric byproducts of this reaction are carbon dioxide and acetic acid.

Microwave-assisted catalytic allylation of aldehydes promoted by a mesoporous silica-supported BINOL ligand in solid media

An efficient and operationally simple method for catalytic allylation has been developed and its application in the microwave-assisted catalytic allylation of aldehydes in solid media was investigated.

Chiral palladium bis(phosphite) PCP-pincer complexes via ligand C–H activation

The synthesis of a range of chiral palladium bis(phosphite) pincer complexes has been achieved via C-H activation of the parent ligands and one of the complexes formed shows good activity in the catalytic allylation of aldehydes.

Bismuth Sulfonate Immobilized on Silica Gel for Allylation of Aldehydes and Synthesis of Homoallylic Amines

Catalytic allylation of aldehydes and the synthesis of homoallylic amines using bismuth sulfonate immobilized on silica gel in presence of allyltributylstannane are reported for the first time. The reaction proceeds smoothly with the aid of benzoic acid as an additive and provides corresponding homoallylic alcohols and homoallylic amines in good yields. The catalyst can be reused five times without significant loss of the catalytic activity.

Enhancement of Lewis Acidity by Ligand‐Defined Metal Geometry: A Catalytic Allylation of Aldehydes with Allyltrimethylsilane.

A highly Lewis acidic aluminum complex was produced using a tridentate ligand 1. The enhanced Lewis acidity of 1-Al was attributed to the combination of a stereoelectronic effect and an electrostatic effect. Comparison with an unstrained complex 4-Al indicated that the ligand-defined sp 3 geometry of the aluminum in 1-Al led to the lower LUMO level and the larger LUMO coefficient on the aluminum. 1-Al promotes a catalytic allylation of aromatic aldehydes using allyltrimethylsilane. A catalytic amount of excess ligand added to the aluminum was important for high chemical yield. The excess ligand might act as a proton source to facilitate ligand exchange on the highly Lewis acidic aluminum.

Catalytic Allylation of Aldehydes with Allyltrimethylsilane Using in situ-Generated Trimethylsilyl Methanesulfonate (TMSOMs) as a Catalyst

Catalytic Allylation of Aldehydes with Allyltrimethylsilane Using in situ-Generated Trimethylsilyl Methanesulfonate (TMSOMs) as a Catalyst

π‐アリルパラジウム錯体を用いる有機合成のルネッサンス

π-Allylpalladium complexes have an electrophilic character and have been widely utilized for the catalytic C-C bond formation reaction with various nucleophiles in Organic Synthesis. We found that the reaction of allylic stannanes with aldehydes proceeded in the presence of palladium catalysts. Detailed investigation revealed that bis-π-allylpalladium complexes, which are a key intermediate in this reaction, have a nucleophilic character. This review describes the unprecedented reactions of the bis-π-allylpalladium complexes : (1) Catalytic allylation of aldehydes and imine. (2) Chemoselective allylation of imines in the presence of aldehydes. (3) Catalytic asymmetric allylation of imines. (4) Catalytic amphiphilic allylation.