Silver Acetate Mediated Acetoxylations of Alkyl Halides

Abstract

Silver acetate promotes the acetoxylation of alkyl halides under neutral reaction conditions. The reaction is applicable to primary and activated secondary alkyl halides, and 2,2-dibromoacetophenones for preparing the corresponding acetates in good yields. The presence of ester, amide, nitrile, hydroxy, and OTBDMS functions on the substrate is tolerated.

En Route to Recyclable Semi-Heterogeneous Photocatalysis with Photoinert CeCl3

“…Following refluxing conditions for 20 h in acetonitrile, treatment of 3g with silver acetate resulted in the formation of a yellow liquid, specifically 2-(4-(tert-butyl)phenyl)-2-oxoethane-1,1-diyl diacetate (5a), with a yield of 85% (Figure 8a). 57 Figure 8b shows the nucleophilic displacement of the bromides of 3b by pyrrolidines, which led to the formation of 2,2-di(pyrrolidin-1-yl)-1-(p-tolyl)ethan-1-one (5b) with a yield of 79%. 58 By following the procedure outlined in Figure 8c, 2-oxo-2-(p-tolyl)ethane-1,1-diyl bis(4-methylbenzenesulfonate) (5c) was obtained with a yield of 87%.…”

“…Figure displays the synthetic modifications of gem -dibromoketones. Following refluxing conditions for 20 h in acetonitrile, treatment of 3g with silver acetate resulted in the formation of a yellow liquid, specifically 2-(4-( tert -butyl)­phenyl)-2-oxoethane-1,1-diyl diacetate ( 5a ), with a yield of 85% (Figure a) Figure b shows the nucleophilic displacement of the bromides of 3b by pyrrolidines, which led to the formation of 2,2-di­(pyrrolidin-1-yl)-1-( p -tolyl)­ethan-1-one ( 5b ) with a yield of 79% .…”

Hypervalent Iodine-Mediated Diastereoselective α-Acetoxylation of Cyclic Ketones

“…Therefore, considerable efforts have been made in the development of synthetic protocols for α-acetoxylation of ketones (Scheme 1). Traditional methods to prepare α-acetoxy ketones are the acetolysis of α-diazo ketone (Newman and Beal, 1950;Erickson et al, 1951;Corey and Knapp, 1976;Kitamura et al, 2012;Wang et al, 2014;Tan et al, 2016;Yuan et al, 2016;Zhang et al, 2016;Hu et al, 2018), α-bromo ketone (Tanner et al, 1991;Valgimigli et al, 2003;Ahmed and Langer, 2006;Chen et al, 2013Chen et al, , 2016Nolla-Saltiel et al, 2014;Carneiro et al, 2015;Liu et al, 2016;Yuan et al, 2019), and in situ generated α-iodo derivatives (Du et al, 2015;Ren et al, 2016;Chen et al, 2017;Tan et al, 2017;Pogaku et al, 2019), which usually require the pre-functionalization of ketones (Scheme 1A). In contrast, umpolung reactions have taken a prominent place for the direct α-oxygenation of carbonyl compounds via oxidation of the enolates or related derivatives with transition metal complexes (Littler, 1962;Heiba and Dessau, 1971;Ng and Henry, 1976;Rubottom et al, 1983;El-Qisairi and Qaseer, 2002;Hamed et al, 2012), or hypervalent iodine reagents (Mizukami et al, 1978;Nicolaou et al, 2002;Bogevig et al, 2004;Sunden et al, 2004;Ochiai et al, 2005;Huang et al, 2007;Yu et al, 2010;…”