Efficient and Practical Ag-Catalyzed Cycloadditions between Arylimines and the Danishefsky Diene

Abstract

An efficient Ag-catalyzed method for asymmetric addition of the Danishefsky diene to various aryl imines to afford cycloadducts in > or =89% ee and > or =85% isolated yield is reported. Reactions are effected with 0.1-1 mol % catalyst (4 degrees C), and the chiral ligand is readily prepared from commercially available materials, including the inexpensive i-Leu. These catalytic asymmetric cycloadditions can be carried out without the use of solvent or with undistilled THF in air. A first generation supported chiral catalyst that effectively promotes the cycloaddition reaction and can be recycled (five cycles) is described.

Organonitrile ligated silver complexes with perfluorinated weakly coordinating anions and their catalytic application for coupling reactions

“…4 In spite of the fact that heterogeneous silver-catalyzed olefin epoxidation is one of the most important and thoroughly investigated industrial processes, 5 homogeneous catalytic processes mediated by silver(I) are relatively rare. Reports on silver(I)-catalyzed processes include carbon-hydrogen insertion, 6 carbon-halogen bond activation, 7 aziridination, 8 silacyclopropanation, 9 ketone-hydroxylation reactions, 10 cyclopropanation 11 and propargylic amine synthesis. 12 Silver ions with weakly coordinating anions are normally used as metathesis reagents and starting materials for the synthesis of asymmetric catalysts 13 and supramolecules.…”

Direct Catalytic Enantioselective Aza‐Diels–Alder Reactions

“…For example, the research groups of Kobayashi and Jørgensen have successfully used chiral Lewis acid complexes as catalysts for these transformations. [5][6][7] However, there is to our knowledge no report of a direct catalytic enantioselective aza-Diels-Alder reaction. Organocatalysis is a rapidly growing research field and has been applied successfully to several different enantioselective reactions.…”

A Silver‐Catalyzed Intramolecular Amidation of Saturated CH Bonds

“…[20][21][22][23] In particular, several nonradical oxidative group-transfer reactions catalyzed by silver were discovered. [24][25][26][27] We reported a disilver(i) compound (1, Scheme 1 a) that efficiently catalyzes the aziridination of olefins.…”