N-phosphino-p-tolylsulfinamide ligands: synthesis, stability, and application to the intermolecular Pauson-Khand reaction.
Here we synthesized a family of racemic and optically pure N-phosphino-p-tolylsulfinamide (PNSO) ligands. Their stability and coordination behavior toward dicobalt-alkyne complexes was evaluated. Selectivities of up to 3:1 were achieved in the ligand exchange process with (mu-TMSC2H)Co2(CO)6. The resulting optically pure major complexes were tested in the asymmetric intermolecular Pauson-Khand reaction and yielded up to 94% ee. X-ray studies of the major complex 18a indicated that the presence of an aryl group on the sulfinamide reduces the hemilabile character of the PNSO ligands.
Revés
Marc
M
Unitat de Recerca en Síntesi Asimètrica (URSA-PCB), Institute for Research in Biomedicine, Universitat de Barcelona, c/Baldiri Reixac 10, E-08028 Barcelona, Spain.
Achard
Thierry
T
Solà
Jordi
J
Riera
Antoni
A
Verdaguer
Xavier
X
D001880:Boranes / Q000737:chemistry; D003035:Cobalt / Q000737:chemistry*; D018360:Crystallography, X-Ray; D008024:Ligands; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D013237:Stereoisomerism; D013449:Sulfonamides / Q000138:chemical synthesis* / Q000737:chemistry*; D014050:Toluene / Q000138:chemical synthesis* / Q000737:chemistry*
D001880:Boranes; D008024:Ligands; C532718:N-phosphino-p-tolylsulfinamide; D009942:Organometallic Compounds; D013449:Sulfonamides; D014050:Toluene; D003035:Cobalt