Addition reactions of heteroatom-COX (X = OR, NR2, COOR) species with alkynes

Tanaka, Masato; Hua, Ruimao

doi:10.1351/pac200274010181

Pure Appl. Chem., 2002, Vol. 74, No. 1, pp. 181-186

http://dx.doi.org/10.1351/pac200274010181

Addition reactions of heteroatom-COX (X = OR, NR2, COOR) species with alkynes

Masato Tanaka^1,2 and Ruimao Hua²

¹ Tokyo Institute of Technology, Chemical Resources Laboratory, 4259 Nagatsuda, Midori-ku, Yokohama 226-8503, Japan
² National Institute of Advanced Industrial Science and Technology, Tsukuba Central 5, Tsukuba, Ibaraki 305-8565, Japan

Abstract: Heteroatom-COX species where the heteroatom is Cl, S, or Sn and X is alkoxy, amino, or alkoxycarbonyl group were found to add to the triple bond of alkynes regio- and stereoselectively in the presence of Rh, Pd, or Ni catalyst. Scope and limitation of these synthetic reactions were disclosed. Mechanistic study revealed that oxidative addition of these heteroatom-COX bonds readily took place and the resulting adducts were isolable and characterized by X-ray diffraction analysis. Synthetic applications of the catalytic reactions were also demonstrated.