Expeditious synthesis of TADDOL-derived phosphoramidite and phosphonite ligands

A simple and reliable protocol for the synthesis of TADDOL-derived monodentate ligands is reported. The reaction of the requisite TADDOL with PCl3 is immediately followed by the treatment of the crude intermediate with both nitrogen and carbon nucleophiles. Several previously unknown or difficult-to-make phosphoramidite and phosphonite ligands L1–L3 and L4–L9 were accessed using this novel procedure.

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(1R,7R)-4-(2,2,6,6-Tetramethylpiperidin-1-yl)-9,9-dimethyl-2,2,6,6-tetraphenyl-3,5,8,10-tetraoxa-4-phosphabicyclo[5.3.0]decaneC40H46NO4P[α]D20=-102 (c 0.985, CHCl3)Source of chirality: l-(+)-tartaric acidAbsolute configuration: (R,R)

(1R,7R)-4-(2,2,6,6-Tetramethylpiperidin-1-yl)-9,9-dimethyl-2,2,6,6-tetrakis(3,5-dimethylphenyl)-3,5,8,10-tetraoxa-4-phosphabicyclo[5.3.0]decaneC48H62NO4P[α]D20=-80.1 (c 1.03, CHCl3)Source of chirality: l-(+)-tartaric acidAbsolute configuration: (R,R)

(1R,7R)-4-(Diisopropylamino)-9,9-dimethyl-2,2,6,6-tetraphenyl-3,5,8,10-tetraoxa-4-phosphabicyclo[5.3.0]decaneC37H42NO4P[α]D20=-96.2 (c 1.00, CHCl3)Source of chirality: l-(+)-tartaric acidAbsolute configuration: (R,R)

(1R,7R)-9,9-Dimethyl-2,2,4,6,6-penta(naphthalen-2-yl)-3,5,8,10-tetraoxa-4-phosphabicyclo[5.3.0]decaneC57H43O4P[α]D20=-109 (c 0.305, CHCl3)Source of chirality: l-(+)-tartaric acidAbsolute configuration: (R,R)

(1R,7R)-4-tert-Butyl-9,9-dimethyl-2,2,6,6-tetra-(naphthalen-2-yl)-3,5,8,10-tetraoxa-4-phosphabicyclo[5.3.0]decaneC51H45O4P[α]D20=-95.2 (c 1.05, CHCl3)Source of chirality: l-(+)-tartaric acidAbsolute configuration: (R,R)

(1R,7R)-4-tert-Butyl-9,9-dimethyl-2,2,6,6-tetra-(o-tolyl)-3,5,8,10-tetraoxa-4-phosphabicyclo[5.3.0]decaneC39H45O4P[α]D20=-89.7 (c 1.00, CHCl3)Source of chirality: l-(+)-tartaric acidAbsolute configuration: (R,R)

(1R,7R)-4-tert-Butyl-9,9-dimethyl-2,2,6,6-tetrakis[3,5-bis(trifluoromethyl)phenyl]-3,5,8,10-tetraoxa-4-phosphabicyclo[5.3.0]decaneC43H29F24O4P[α]D20=-38.4 (c 0.645, CHCl3)Source of chirality: l-(+)-tartaric acidAbsolute configuration: (R,R)

(1R,7R)-4-tert-Butyl-2,2,6,6,9,9-hexaphenyl-3,5,8,10-tetraoxa-4-phosphabicyclo[5.3.0]decaneC45H41O4P[α]D20=+28.4 (c 0.295, CHCl3)Source of chirality: l-(+)-tartaric acidAbsolute configuration: (R,R)

(1R,7R)-9,9-Dimethyl-2,2,6,6-tetraphenyl-4-(7-picolyl)-3,5,8,10-tetraoxa-4-phosphabicyclo[5.3.0]decaneC37H34NO4P[α]D20=-118 (c 0.430, CHCl3)Source of chirality: l-(+)-tartaric acidAbsolute configuration: (R,R)