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New Entries in Lewis Acid−Lewis Base Bifunctional Asymmetric Catalyst: Catalytic Enantioselective Reissert Reaction of Pyridine Derivatives

2004; American Chemical Society; Volume: 126; Issue: 38 Linguagem: Inglês

10.1021/ja045966f

1943-2984

Eiko Ichikawa, Masato Suzuki, Kazuo Yabu, Matthias Albert, Motomu Kanai, Masakatsu Shibasaki,

Synthetic Organic Chemistry Methods

The first catalytic enantioselective Reissert reaction of pyridine derivatives that affords products with excellent regio- and enantioselectivity is described. The key for success is the development of new Lewis acid−Lewis base bifunctional asymmetric catalysts containing an aluminum as a Lewis acid and sulfoxides or phosphine sulfides as a Lewis base. These reactions are useful for the synthesis of a variety of chiral piperidine subunits, and catalytic enantioselective formal synthesis of CP-293,019, a selective D4 receptor antagonist, was achieved. Preliminary mechanistic studies indicated that both sulfoxides and phosphine sulfides can activate TMSCN as a Lewis base. In addition, the sulfoxides with appropriate stereochemistry might stabilize a highly enantioselective bimetallic complex (a presumed active catalyst) through internal coordination to aluminum.