New entries in Lewis acid-Lewis base bifunctional asymmetric catalyst: catalytic enantioselective Reissert reaction of pyridine derivatives.
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.
Ichikawa
Eiko
E
Graduate School of Pharmaceutical Sciences, The University of Tokyo, Tokyo 113-0033, Japan.
Suzuki
Masato
M
Yabu
Kazuo
K
Albert
Matthias
M
Kanai
Motomu
M
Shibasaki
Masakatsu
M
D000535:Aluminum / Q000737:chemistry; D002384:Catalysis; D007546:Isoquinolines / Q000737:chemistry*; D009284:Naphthols / Q000737:chemistry; D010087:Oxides / Q000737:chemistry; D010720:Phosphines / Q000737:chemistry; D010880:Piperidines / Q000138:chemical synthesis* / Q000737:chemistry; D011719:Pyrazines / Q000138:chemical synthesis; D011725:Pyridines / Q000138:chemical synthesis* / Q000737:chemistry; D011743:Pyrimidines / Q000138:chemical synthesis; D011804:Quinolines / Q000737:chemistry*; D013237:Stereoisomerism
C406944:BINOL, naphthol; C111732:CP 293019; D007546:Isoquinolines; D009284:Naphthols; D010087:Oxides; D010720:Phosphines; D010880:Piperidines; D011719:Pyrazines; D011725:Pyridines; D011743:Pyrimidines; D011804:Quinolines; D000535:Aluminum; C044646:phosphine