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-symmet- ric cycloglycerophosphates (cGPAs) and their appli- cation 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.

Design, Synthesis and Application of C2-Symmetric Cycloglycerodiphosphate Catalysts

Achille Antenucci
First
;
Giovanni Ghigo;Stefano Dughera
Last
2023-01-01

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-symmet- ric cycloglycerophosphates (cGPAs) and their appli- cation 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.
2023
365
1170
1178
https://onlinelibrary.wiley.com/doi/full/10.1002/adsc.202300136
asymmetric organocatalysis; enantioselectivity; DFT studies; organic synthesis; phosphorous heterocycles
Achille Antenucci; Giovanni Ghigo; Davide Cassetta; Marco Alcibiade; Stefano Dughera
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2318/1902312
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