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An Atropisomerically Enforced Phosphoric Acid for Organocatalytic Asymmetric Reactions
Author(s) -
Bernardi Luca,
Bolzoni Giada,
Fochi Mariafrancesca,
Mancinelli Michele,
Mazzanti Andrea
Publication year - 2016
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201600296
Subject(s) - atropisomer , chemistry , diastereomer , enantioselective synthesis , phosphoric acid , organocatalysis , catalysis , circular dichroism , chirality (physics) , combinatorial chemistry , stereochemistry , organic chemistry , nambu–jona lasinio model , chiral symmetry breaking , physics , quantum mechanics , quark
Three BINOL‐derived phosphoric acids exhibiting atropisomerism in the 3,3′‐positions were obtained by Suzuki coupling reaction. The diastereomeric mixture was resolved by HPLC. Structural assignment was achieved by NOE‐NMR analysis and by TD‐DFT simulation of the electronic circular dichroism (ECD) spectra. The three atropisomeric catalysts were tested in three enantioselective reactions, comparing their ability to induce enantioselectivity with related, well‐known, phosphoric acid structures. All three catalysts were competent in promoting the reactions, rendering excellent enantioselectivity (98 % ee ) in one case. The atropisomeric features at the 3,3′‐position were indeed found to influence the outcome of the reaction, demonstrating the potential of atropisomeric conformational control at the 3,3′‐position of the BINOL core in the rationalization of catalyst performances and in the design of new efficient structures.