194733-29-4Relevant academic research and scientific papers
Manganese-Catalyzed Acceptorless Dehydrogenative Coupling of Alcohols with Sulfones: A Tool to Access Highly Substituted Vinyl Sulfones
Barman, Milan K.,Maji, Biplab,Waiba, Satyadeep
, p. 973 - 982 (2021/08/24)
The development of first-row-transition-metal catalysts that can match with the reactivities of the noble metals is considered to be challenging yet very much a desirable goal in homogeneous catalysis. It has become even more fascinating to develop processes where these metals show a unique reactivity and selectivity than their higher congeners. Herein, we report on the catalytic activity of a pincer complex of the abundant earth metal manganese for an unprecedented acceptorless dehydrogenative coupling of alkyl sulfones with alcohols. Thus, highly functionalized vinyl sulfones were obtained in moderate to good yields. Both benzylic and aliphatic alcohols could be utilized, and several functional groups including bromides and iodides are tolerated under the reaction conditions. The reaction is environmentally benign, producing dihydrogen and water as byproducts. Preliminary mechanistic experiments involving kinetic, deuterium-labeling, and NMR experiments were performed.
Palladium-catalyzed substitution and cross-coupling of benzylic fluorides
Blessley, George,Holden, Patrick,Walker, Matthew,Brown, John M.,Gouverneur, Veronique
, p. 2754 - 2757 (2012/07/16)
Benzylic fluorides are suitable substrates for Pd(0)-catalyzed Tsuji-Trost substitution using carbon, nitrogen, oxygen, and sulfur nucleophiles and for cross-coupling with phenylboronic acid. For the bifunctional substrate 4-chlorobenzyl fluoride, fine-tuning of the reaction conditions allows for the regioselective displacement of either the chlorine or fluorine substituent. The leaving group ability of fluoride vs other groups displaced in substitution is CF3CO2 ≈ p-NO2C6H 4CO2 ≈ OCO2CH3 > F > CH3CO2, a ranking similar to allylic fluorides under Pd catalysis.
Equilibrium acidities of some sulfones and sulfoxides in tetrahydrofuran
Streitwieser, Andrew,Wang, George Peng,Bors, Daniel A.
, p. 10103 - 10112 (2007/10/03)
Ion pair acidities are reported in tetrahydrofuran (THF) solution for the lithium and cesium salts of several sulfones and one sulfoxide. These salts are shown to be monomeric in the THF solutions studied. Thermodynamic constants are reported for several salts. The results and some conductivity studies show that both the lithium and cesium salts are contact ion pairs in THF. Because of ion association the relative pKs are slightly lower for cesium salts and much lower for lithium salts than for the free ions in DMSO solution.
