Isolable gold(I) complexes having one low-coordinating ligand as catalysts for the selective hydration of substituted alkynes at room temperature without acidic promoters.
Hydration of a wide range of alkynes to the corresponding ketones has been afforded in high yields at room temperature by using gold(I)-phosphine complexes as catalyst, with no acidic cocatalysts required. Suitable substrates covering alkyl and aryl terminal alkynes, enynes, internal alkynes, and propargylic alcohols, including enantiopure forms, are cleanly transformed to the corresponding ketones in nearly quantitative yields. Acid-labile groups present in the substrates are preserved. The catalytic activity strongly depends on both the nature of the phosphine coordinated to the gold (I) center and the softness of the counteranion, the complex AuSPhosNTf(2) showing the better activity. A plausible mechanism for the hydration of alkynes through ketal intermediates is proposed on the basis of kinetic studies. The described catalytic system should provide an efficient alternative to mercury-based methodologies and be useful in synthetic programs.
Leyva
Antonio
A
Instituto de Tecnología Química UPV-CSIC, Avda. de los Naranjos s/n, 46022, Valencia, Spain. anleyva@itq.upv.es
Corma
Avelino
A
D000447:Aldehydes / Q000138:chemical synthesis* / Q000737:chemistry; D000480:Alkynes / Q000737:chemistry*; D002384:Catalysis; D007659:Ketones / Q000138:chemical synthesis* / Q000737:chemistry; D008024:Ligands; D015394:Molecular Structure; D050607:Organogold Compounds / Q000737:chemistry*; D013237:Stereoisomerism; D013696:Temperature; D014867:Water / Q000737:chemistry
D000447:Aldehydes; D000480:Alkynes; D007659:Ketones; D008024:Ligands; D050607:Organogold Compounds; D014867:Water