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A New Chiral P,N‐Ligand Derived from 1‐Phenylphospholane‐2‐carboxylic Acid (Phenyl‐P‐proline) for Palladium‐Catalyzed Asymmetric Allylic Substitution Reactions
Author(s) -
Sun XiangMin,
Koizumi Masatoshi,
Manabe Kei,
Kobayashi Shū
Publication year - 2005
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.200505234
Subject(s) - chemistry , allylic rearrangement , ligand (biochemistry) , palladium , medicinal chemistry , denticity , substitution reaction , stereochemistry , carboxylic acid , enantioselective synthesis , catalysis , nucleophile , organic chemistry , crystal structure , receptor , biochemistry
New types of P,N‐ligands, cis ‐ and trans ‐ 3 , containing a tetrahydroisoquinoline skeleton as an N‐donor were synthesized from (1 R ,2 S )‐1‐phenylphospholane‐2‐carboxylic acid (phenyl‐P‐proline, 1 ). The cis isomer, cis ‐ 3 , was found to act as an excellent ligand in palladium‐catalyzed asymmetric allylic substitution reactions. The reactions of 1,3‐diphenyl‐2‐propenyl acetate ( 5 ) with several nucleophiles in the presence of [Pd(π‐allyl)Cl] 2 , cis ‐ 3 (Pd : ligand=1 : 2), and a base afforded the desired products in high yields with high enantioselectivity. It was suggested that these ligands did not serve as P,N‐bidentate ligands but as P‐monodentate ligands in these reactions.