The coordination chemistry and reactivity of amino-dithiaphospholanes with rhodium, iridium, and ruthenium

• Published in: Tetrahedron letters 2009-02, Vol.50 (8), p.922-925
• Main Authors: Costin, Stephen, Sedinkin, Sergey L., Bauer, Eike B.
• Format: Article
• Language: English
• Subjects: Amino-dithiaphospholanes; Iridium; Nicholas reaction; Phosphoramidites; Rhodium; Ruthenium
• ISSN: 0040-4039; 1873-3581
• DOI: 10.1016/j.tetlet.2008.12.034

Novel amino-dithiaphospholane complexes of ruthenium, iridium, and rhodium were synthesized, and their properties were studied. Reaction of the new amino-dithiaphospholane (RS) 2 PNR 2 ′ (R = binaphthyl, R′ = CH 2Ph, (rac)- 4) with [RuCl 2( p-cymene)] 2 afforded [RuCl 2( p-cymene)((rac)- 4)] in 67% isolated yield. Similarly, the new amino-dithiaphospholanes (RS) 2 PNR 2 ′ (R = cyclohexyl, (rac)- 7) and (RS) 2 PNR 2 ′ (R = phenyl, 9) gave upon reaction with [RhCl(CO) 2] 2 and [IrCp ∗Cl 2] 2 the novel complexes [RhCl(CO)(L) 2] and [IrCp ∗Cl 2(L)] (L = (rac)- 7, 9) in 61–96% yields. The ruthenium complex is catalytically active for the etherification of propargylic alcohols with methanol and ethanol (8–48 h, 90 °C, 40–85% isolated yields).