110366-21-7Relevant academic research and scientific papers
Silver(I)-Catalyzed Addition of Phenols to Alkyne Cobalt Cluster Stabilized Carbocations
Valderas, Carolina,Casarrubios, Luis,Lledos, Agusti,Ortu?o, Manuel A.,de la Torre, María C.,Sierra, Miguel A.
supporting information, p. 9015 - 9023 (2016/07/06)
A smooth catalytic method to use phenols as the nucleophilic partner in the Nicholas reaction has been developed. The method uses either AgIor AuIcatalysts with AgClO4or AgBF4as the most efficient catalysts tested. Neither additional additives nor cocatalysts were required and the formation of the corresponding phenol adducts occurred in excellent yields. The process has the single limitation of the inability of less nucleophilic phenols (4-nitrophenol) to generate the corresponding adducts. Additionally, the reaction is highly diastereoselective. DFT calculations allow a catalytic cycle to be proposed that involves trimetallic intermediates; the rate-determining step of the reaction is hydroxy-group elimination in a cobalt–silver trimetallic intermediate.
The gold(I)- and silver(I)-catalyzed nicholas reaction
Valderas, Carolina,De La Torre, Maria C.,Fernandez, Israel,Munoz, Maria Paz,Sierra, Miguel A.
supporting information, p. 951 - 956 (2013/04/23)
The Au(I) and Ag(I) catalytic Nicholas type reaction has been developed for oxygen and carbon nucleophiles. This process occurs with high reaction yields and selectivity, avoiding the main shortcomings of the acid-promoted standard Nicholas reaction. A catalytic reaction pathway involving trimetallic complex intermediates is proposed.
ADDITION OF ORGANOMAGNESIUM REAGENTS TO RING EPOXY-KETONES V. 4,4-DIMETHYL-2,3-EPOXYCYCLOHEXANONE, AND 3,5,5-TRIMETHYL-2,3-EPOXYCYCLOHEXANONE
Sepulveda, Jose,Soriano, Concepcion,Roquet-Jalmar, Joaquin,Mestres, Ramon,Riego, Juan
, p. 189 - 192 (2007/10/02)
Stereoselectivities found for additions of ethynyl, vinyl, and ethylmagnesium bromides to 4,4-dimethylcyclohexanone oxide 4 are in agreement with a biassed 4a conformation of the substrate, and with a torsional strain effect by the oxirane C2-O bond.Thus, a 1:1 mixture is obtained for the small ethynyl group, whereas highly selective cis attack is found for the larger ethyl reagent.Additions to 3,5,5-trimethylepoxycyclohexanone are highly selective for any of the above organomagnesium reagents due to steric hindrance by the axial methyl group at C5, and trans adducts 14, 16 and 18 result, along with a small amount of the cis-ethynyl epoxycyclohexanol 15.Easy trans-hydroxy-epoxy interconversions have been observed for the trans-ethyl adducts 10 and 18, which are obtained along with their respective isomers 12 and 20.
