The synthesis of new chiral P,N-ligands on the basis of camphor

The synthesis of new chiral P,N-ligands has been developed starting from 1,3-dicarbonyls, which are readily available from camphor. Iridium complexes derived from these ligands are also described. Furthermore, some preliminary results related to catalytic hydrogenation with these iridium complexes are presented.

Figure optionsDownload as PowerPoint slide

(4S,7R)-7,8,8-Trimethyl-1-(2-diphenylphosphino-6-methoxyphenyl)-4,5,6,7-tetrahydro-4,7-methano-1H-indazoleC30H31N2OP[α]D21=−3.7 (c 0.5, CH2Cl2)Absolute configuration: (4S,7R)Source of chirality: (IR)-(+)-camphor

(4S,7R)-3,7,8,8-Tetramethyl-1-(2-diphenylphosphino-6-methoxyphenyl)-4,5,6,7-tetrahydro-4,7-methano-1H-indazoleC31H33N2OP[α]D22=+7.5 (c 0.5, CH2Cl2)Absolute configuration: (4S,7R)Source of chirality: (IR)-(+)-camphor

(4S,7R)-7,8,8-Trimethyl-1-(2-dicyclohexylphosphino-6-methoxyphenyl)-4,5,6,7-tetrahydro-4,7-methano-1H-indazoleC30H43N2OP[α]D22=+4.2 (c 0.5, CH2Cl2)Absolute configuration: (4S,7R)Source of chirality: (IR)-(+)-camphor

(4S,7R)-3,7,8,8-Tetramethyl-1-(2-dicyclohexylphosphino-6-methoxyphenyl)-4,5,6,7-tetrahydro-4,7-methano-1H-indazoleC31H45N2OP[α]D22=−12.9 (c 1, ethyl acetate)Absolute configuration: (4S,7R)Source of chirality: (IR)-(+)-camphor

(4S,7R)-7,8,8-Trymethyl-1-[2-(di-o-tolylphosphino)-6-methoxyphenyl]-4,5,6,7-tetrahydro-4,7-methano-1H-indazoleC32H35N2OP[α]D22=−13.2 (c 0.5, CD2Cl2)Absolute configuration: (4S,7R)Source of chirality: (IR)-(+)-camphor

(4S,7R)-3,7,8,8-Tetramethyl-1-[2-(diortotolyphosphino)-6-methoxyphenyl)-4,5,6,7-tetrahydro-4,7-methano-1H-indazoleC33H37N2OP[α]D22=−0.55 (c 1, ethyl acetate)Absolute configuration: (4S,7R)Source of chirality: (IR)-(+)-camphor

(4S,7R)-7,8,8-Trimethyl-1-[2-di(3,5-bistrifluromethylphenyl)phosphino-6-methoxyphenyl]-4,5,6,7-tetrahydro-4,7-methano-1H-indazoleC34H27F12N2OP[α]D23=−8.4 (c 0.5, CD2Cl2)Absolute configuration: (4S,7R)Source of chirality: (IR)-(+)-camphor

(4S,7R)-3,7,8,8-Tetramethyl-1-[2-di(3,5-bistrifluromethylphenyl)phosphino-6-methoxyphenyl]-4,5,6,7-tetrahydro-4,7-methano-1H-indazoleC35H29F12N2OP[α]D23=−13.0 (c 0.5, CD2Cl2)Absolute configuration: (4S,7R)Source of chirality: (IR)-(+)–camphor