P∗,P∗-Bidentate diastereoisomeric bisdiamidophosphites based on N-benzyltartarimide and their applications in asymmetric catalytic processes

Two novel P∗-stereogenic bisdiamidophosphites derived from (3R,4R)-N-benzyltartarimide as a chiral 1,2-diol have been prepared from readily available starting materials. Palladium and rhodium catalytic systems containing these new P∗,P∗-bidentate ligands afforded 96%, 83% and 65% ee in asymmetric allylic substitution, hydrogenation and addition processes, respectively. These diastereomeric diamidophosphites were found to be complementary stereoselectors.

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3,4-Bis[(2′R,5′S)-3′-phenyl-1′,3′-diaza-2′-phosphabicyclo[3.3.0]octyloxy]-(3R,4R)-1-benzylpyrrolidine-2,5-dioneC33H37N5O4P2De = 100%[α]D20=-288.9 (c 1.0, CHCl3)Source of chirality: (S)-(+)-glutamic acid (R,R)-tartaric acidAbsolute configuration: (2′R,5′S,3R,4R)

3,4-Bis[(2′S,5′R)-3′-phenyl-1′,3′-diaza-2′-phosphabicyclo[3.3.0]octyloxy]-(3R,4R)-1-benzylpyrrolidine-2,5-dioneC33H37N5O4P2De = 100%[α]D20=+252.4 (c 1.0, CHCl3)Source of chirality: (R)-(−)-glutamic acid (R,R)-tartaric acidAbsolute configuration: (2′S,5′R,3R,4R)