Abstract

A series of covalently linked bis‐ and trisphosphoric acids was investigated for their application in the stereoselective transfer‐hydrogenation of quinolines. In a combined experimental and theoretical study, it was found that the number and relative positioning of the chiral 1,1′‐binaphthyl‐phosphoric acid groups strongly influences the stereoselectivity of the reaction, based on two competing reaction mechanisms. While a single 3‐monosubstituted phosphoric acid moiety gives rise to little enantioselectivity, correct positioning of two phosphoric acids allows a cooperative mechanism, resulting in significantly higher stereoselectivities.

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