Ruthenium-catalyzed cycloisomerizations of diynols.
A wide variety of diynols containing tertiary, secondary, and primary propargylic alcohols undergo a cycloisomerization reaction to form dienones and dienals in the presence of a catalytic amount of [CpRu(CH(3)CN)(3)]PF(6). The formation of five- and six-membered rings is possible using this methodology. Secondary diynols react to form single geometrical isomeric dienones and -als. Primary diynols undergo a cycloisomerization as well as a hydrative cyclization process. The utility of primary diynol cycloisomerization is demonstrated in a synthesis of (+)-alpha-kainic acid.
Trost
Barry M
BM
Department of Chemistry, Stanford University, Stanford, CA 94305, USA. bmtrost@stanford.edu
Rudd
Michael T
MT
D000447:Aldehydes / Q000138:chemical synthesis*; D000480:Alkynes / Q000138:chemical synthesis / Q000737:chemistry*; D002384:Catalysis; D003500:Cyclization; D003516:Cycloparaffins / Q000138:chemical synthesis*; D007536:Isomerism; D007659:Ketones / Q000138:chemical synthesis*; D020005:Propanols / Q000737:chemistry*; D012428:Ruthenium / Q000737:chemistry
D000447:Aldehydes; D000480:Alkynes; D003516:Cycloparaffins; D007659:Ketones; D020005:Propanols; D012428:Ruthenium; C028255:propargyl alcohol