Design, Synthesis and Application of C2‐Symmetric Cycloglycerodiphosphate Catalysts. Issue 8 (4th April 2023)

• Record Type: Journal Article
• Authors: Antenucci, Achille; Ghigo, Giovanni; Cassetta, Davide; Alcibiade, Marco; Dughera, Stefano
• Is Part Of: Advanced synthesis & catalysis. Volume 365:Issue 8(2023)
• Page Start: 1170
• Page End: 1178
• Publication Date: 2023-04-04
• Subjects: asymmetric organocatalysis -- enantioselectivity -- DFT studies -- organic synthesis -- phosphorous heterocycles; Catalysis -- Periodicals; Organic compounds -- Synthesis -- Periodicals; Chemistry -- Periodicals; Chemistry, Technical -- Periodicals; Chemistry -- Periodicals; Catalysis -- Periodicals; Technology, Pharmaceutical -- Periodicals; 547.2
• DOI: 10.1002/adsc.202300136
• Languages: English
• ISSNs: 1615-4150

Abstract

Abstract: Chiral phosphoric acids (CPAs) and their salts are the privileged catalysts in a plethora of asymmetric transformations. All of the scaffolds of efficient CPAs rely on C2 ‐symmetry and axial chirality, while the only examples of punctually chiral CPAs are TADDOL derivatives. Herein, we present the design and the synthesis of C2 ‐symmetric cycloglycerophosphates (cGPAs) and their application throughout the addition of trimethylsilyl cyanide (TMSCN) to aldehydes and ketones, to obtain the corresponding cyanohydrins in yields between 77 and 99% and ee between 84.2 and 99.5% (27 examples). A DFT computational model is moreover performed to rationalize the reaction mechanism and its stereochemical outcome. Abstract :