25753-16-6Relevant articles and documents
Organocatalytic Desymmetrisation of Fittig's Lactones: Deuterium as a Reporter Tag for Hidden Racemisation
Spránitz, Péter,Soregi, Petra,Botlik, Bence Béla,Berta, Máté,Soós, Tibor
, p. 1263 - 1272 (2019/02/26)
Highly enantioselective desymmetrisation of Fittig's lactones with alcohols is promoted by bifunctional cinchona squaramides. The reactions were carried out with monodeuterated methanol to detect possible hidden racemisation of the stereogenic centre. Current evidence suggests that racemisation was not a relevant process for most substrates; partial erosion of enantioselectivity was only detected with ortho -substituted aryl derivates. The resultant glutaric acid derivatives possess a scaffold that is common in natural products and the compounds are also useful chiral building blocks for further synthetic endeavours.
Sc(OTf)3-catalyzed synthesis of anhydrides from twisted amides
Liu, Yongmei,Liu, Ruzhang,Szostak, Michal
, p. 1780 - 1785 (2017/03/09)
A novel synthesis of anhydrides from twisted amides is reported. Sc(OTf)3 catalysis in the presence of water is used to synthesize anhydrides in one step from amides without external nucleophiles. Mechanistic studies indicate that the coordination of the catalyst is critical to induce the challenging N-C activation step. This process further highlights the utility of twisted amides in organic synthesis. Notably, the reaction indicates that twisted amides based on the glutarimide scaffold are more reactive than carboxylic acid anhydrides under the developed conditions, which opens the door to controlled sequential catalysis through amide N-C bond cleavage.
An effective method for the synthesis of carboxylic esters and lactones using substituted benzoic anhydrides with Lewis acid catalysts
Shiina, Isamu
, p. 1587 - 1599 (2007/10/03)
An efficient mixed-anhydride method for the synthesis of carboxylic esters and lactones using benzoic anhydride having electron withdrawing substituent(s) is developed by the promotion of Lewis acid catalysts. In the presence of a catalytic amount of TiCl2(ClO4)2, various carboxylic esters are prepared in high yields through the formation of the corresponding mixed-anhydrides from 3,5-bis(trifluoromethyl)benzoic anhydride and carboxylic acids. The combined catalyst consisting of TiCl 2(ClO4)2 together with chlorotrimethylsilane functions as an effective catalyst for the synthesis of carboxylic esters from free carboxylic acids and alcohols with 4-(trifluoromethyl)benzoic anhydride. Various macrolactones are prepared from the free ω-hydroxycarboxylic acids by the combined use of 4-(trifluoromethyl)benzoic anhydride and titanium(IV) catalysts together with chlorotrimethylsilane under mild reaction conditions. The lactonization of trimethylsilyl ω-(trimethylsiloxy) carboxylates using 4-(trifluoromethyl)benzoic anhydride is also promoted at room temperature in the presence of a catalytic amount of TiCl 2(ClO4)2. An 8-membered ring lactone, a synthetic intermediate of cephalosporolide D, is successfully synthesized according to this mixed-anhydride method using 4-(trifluoromethyl)benzoic anhydride by the promotion of a catalytic amount of Hf(OTf)4.