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( S )‐2‐[( N ‐arylamino)methyl]pyrrolidines‐Based Phosphoramidite P,N ‐Ligand Library for Asymmetric Metal‐Catalyzed Allylic Substitution and Conjugate 1,4‐Addition
Author(s) -
Gavrilov Konstantin N.,
Mikhel Igor S.,
Chuchelkin Ilya V.,
Zheglov Sergey V.,
Gavrilov Vladislav K.,
Birin Kirill P.,
Tafeenko Victor A.,
Chernyshev Vladimir V.,
Goulioukitaliya S.,
Beletskaya Irina P.
Publication year - 2016
Publication title -
chemistryselect
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.437
H-Index - 34
ISSN - 2365-6549
DOI - 10.1002/slct.201600964
Subject(s) - phosphoramidite , chemistry , desymmetrization , allylic rearrangement , denticity , catalysis , ligand (biochemistry) , medicinal chemistry , stereochemistry , diethylzinc , carbon 13 nmr , substitution reaction , proton nmr , enantioselective synthesis , metal , organic chemistry , oligonucleotide , biochemistry , receptor , dna
Abstract A library of easy‐to‐prepare and modular chiral P,N ‐phosphoramidites based on [1,1′‐biaryl]‐2,2′‐diols and C 1 ‐symmetric 1,2‐diamines has been designed and developed. The structures of the novel ligands have been elucidated by means of 2D‐NMR and confirmed in the solid state by X‐ray diffraction analysis. Stereoselectors of this type exhibited high enantioselectivities in Pd‐catalyzed allylic substitution reactions of ( E )‐1,3‐diphenylallyl acetate with NaSO 2 p Tol (up to 91 % ee ), CH 2 (CO 2 Me) 2 (up to 89 % ee ), (C 3 H 7 ) 2 NH (up to 94 % ee ) and (EtO) 2 P(O)CH 2 NH 2 as a novel nucleophile (up to 98 % ee ). Ee values of up to 88 % and 72 % have been obtained in the Pd‐catalyzed desymmetrization of N,N′ ‐ditosyl‐ meso ‐cyclopent‐4‐ene‐1,3‐diol biscarbamate and in the Cu‐catalyzed 1,4‐conjugate addition of diethylzinc to chalcone, respectively. The reactions of P,N ‐bidentate ligands with [Pd(Cod)Cl 2 ] at molar ratios of L/M=1 and 2 have been studied using 1 H, 13 C, 13 C‐ 1 H HSQC, 13 C‐ 1 H HMBC, 1 H‐ 1 H COSY, 1 H‐ 1 H ROESY, DOSY and 31 P NMR spectroscopy as well as HR ESI mass spectrometry.