The addition reaction of chloroacetyl chloride derivatives with terminal alkynes was found to be catalyzed by Rh(acac)(CO)(AsPh(3)) to afford (Z)-1,4-dichloro-3-buten-2-one derivatives, which displayed diverse reactivities in synthetic elaboration.
Organo-phosphorus compounds S 0080 Palladium-Complex-Catalyzed Regioselective Markovnikov Addition Reaction and Dehydrogenative Double Phosphinylation to Terminal Alkynes with Diphenylphosphine Oxide. -It is demonstrated that the catalyst ligand plays a key role for product distribution. -(DOBASHI, N.; FUSE, K.; HOSHINO, T.; KANADA, J.; KASHIWABARA, T.; KOBATA, C.; NUNE, S. K.; TANAKA*, M.; Tetrahedron Lett. 48 (2007) 27, 4669-4673; Chem. Resour. Lab., Tokyo Inst. Technol., Yokohama 226, Japan; Eng.) -Mais 42-169
Halogen compounds P 0030Rhodium-Complex-Catalyzed Addition Reactions of Chloroacetyl Chlorides to Alkynes. -The reaction with various terminal alkynes proceeds with mostly high (Z)-selectivity. The reaction is not applicable to the internal alkynes and conjugate substrates resulting in oligomerization. The synthetic utility of product (VIIa) is demonstrated. -(KASHIWABARA, T.; FUSE, K.; HUA, R.; TANAKA*, M.; Org. Lett. 10 (2008) 23, 5469-5472; Chem. Resour. Lab., Tokyo Inst. Technol., Yokohama 226, Japan; Eng.) -R. Steudel 17-058
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