title: Use of group 4 bis(sulfonamido) complexes in the intramolecular hydroamination of alkynes and allenes.
abstract: Titanium tetrakis(amido) complexes catalyze the intramolecular hydroamination of alkynes and allenes more efficiently than Cp-based species. We report here that electron-withdrawing and sterically demanding bis(sulfonamido) ligands lead to enhanced catalytic activity. Zirconium analogues have also been prepared, and the tosyl-substituted complex 20 has been structurally characterized. As in the titanium series, bis(sulfonamido) zirconium catalysts are more efficient in the intramolecular hydroamination of allenes than bis(cyclopentadienyl) complex Cp(2)ZrMe(2) (23). Furthermore, these compounds transform 1,3-disubstituted aminoallenes with high stereoselectivity to the Z-allylamines and allow the hydroamination of a trisubstituted allene. Titanium bis(sulfonamido) imido complex 27 was synthesized. It converts aminoallene 10 to cylic imine 11 with a rate comparable to that of tetrakis(amide) 15, supporting the hypothesis of a catalytically active titanium imido intermediate.
mesh_terms: D000475:Alkenes / Q000737:chemistry*; D000480:Alkynes / Q000737:chemistry*; D000586:Amination; D018360:Crystallography, X-Ray; D003500:Cyclization; D009942:Organometallic Compounds / Q000737:chemistry; D013449:Sulfonamides / Q000737:chemistry*; D014025:Titanium / Q000737:chemistry*; D015040:Zirconium / Q000737:chemistry*
chemical_list: D000475:Alkenes; D000480:Alkynes; D009942:Organometallic Compounds; D013449:Sulfonamides; D015040:Zirconium; D014025:Titanium