Diverse "roof shaped" chiral diamidophosphites: palladium coordination and catalytic applications. (5th January 2022)

• Record Type: Journal Article
• Authors: Gavrilov, Konstantin N.; Chuchelkin, Ilya V.; Gavrilov, Vladislav K.; Zheglov, Sergey V.; Firsin, Ilya D.; Trunina, Valeria M.; Zamilatskov, Ilya A.; Tyurin, Vladimir S.; Tafeenko, Victor A.; Chernyshev, Vladimir V.; Zimarev, Vladislav S.; Goulioukina, Nataliya S.
• Is Part Of: New journal of chemistry. Volume 46:Number 4(2022)
• Page Start: 1751
• Page End: 1762
• Publication Date: 2022-01-05
• Subjects: Chemistry -- Periodicals; Chimie -- Périodiques; 540
• DOI: 10.1039/d1nj05143a
• Languages: English
• ISSNs: 1144-0546

Abstract

Abstract : "Roof shaped" chiral diamidophosphites of various structures and denticities were obtained and tested in Pd-catalyzed asymmetric allylic substitution. Abstract : A series of diamidophosphite ligands of various structures and denticities were synthesized from (11 S, 12 S )-bis(hydroxymethyl)-9, 10-dihydro-9, 10-ethanoanthracene as a "roof shaped" 1, 4-diol. On the basis of these ligands, we obtained three types of Pd(II) allylic complexes: a P, P -chelate, a P, S -bridged head-to-tail dinuclear complex, and complexes each containing a pair of P -monodentately coordinated P -, P, N - or P, S -ligands. The structures of the ligands and their complexes were determined using 2D NMR spectroscopy. Four diamidophosphites were also characterized via their X-ray structural data. This kind of stereoselector exhibited up to 98% ee in the Pd-mediated allylic substitution of ( E )-1, 3-diphenylallyl acetate with C- and N-nucleophiles. In the Pd-catalyzed allylic alkylation of cinnamyl acetate with various C-nucleophiles, ee values of up to 90% were obtained. In addition, up to 71% ee was achieved in the Pd-catalyzed asymmetric amination of 2-(diethoxyphosphoryl)-1-phenylallyl acetate with aniline, which is a pioneering example of diamidophosphite-type ligand involvement in this challenging reaction. The effects of the diamidophosphite moiety and the denticity of the ligands on the catalytic activity and enantioselectivity were investigated.