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Syntheses and Coordination Chemistry of Chiral Phosphanyl Glycerols and Their Derivatives – X‐ray Structure of ( R )‐Ph 2 P–CH 2 –C a H–O–B(Ph)–O–C b H 2 ( C a – C b )
Author(s) -
Brauer David J.,
Machnitzki Peter,
Nickel Thomas,
Stelzer Othmar
Publication year - 2000
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/(sici)1099-0682(200001)2000:1<65::aid-ejic65>3.0.co;2-1
Subject(s) - chemistry , diastereomer , denticity , asymmetric carbon , medicinal chemistry , enantioselective synthesis , nucleophile , phenylboronic acid , stereochemistry , organic chemistry , crystal structure , catalysis , alkyl
Reaction of ( R )‐(+)‐2,3‐epoxy‐1‐propanol with Ph 2 PH, Ph(Me)PH, or PhPH 2 in the superbasic medium KOH/DMSO affords the novel chiral phosphanes 1a – 1c . While 1a is obtained enantiomerically pure, 1b and the secondary phosphane 1c are formed as mixtures of diastereoisomers ( R P R C , S P R C ) with homochiral β carbon atoms. Derivatization of 1a with phenylboronic acid or 2,2‐dimethoxypropane yields 2a and 3a with 1,3,2‐dioxaborolane and 1,3‐dioxolane ring systems, respectively. The X‐ray structure of 2a (space group P 2 1 ) reveals the presence of four molecules of R configuration in the unit cell. Nucleophilic phosphanylation of ( R )‐(–)‐2,3‐ O ‐isopropylideneglycerol tosylate with Ph 2 PH, Ph(Me)PH, or PhPH 2 yields chiral 3a – 3d . Compound 3b was obtained enantiomerically pure. The secondary phosphane 3c has been employed in syntheses of the hydrophilic tertiary phosphanes 3e , 3f and of the novel bidentate phosphane ligands 3g , 3h , all of which have homochiral β carbon atoms. Pd II complexes PdL 2 Cl 2 of 1a , 2a , 3a (L) are formed as mixtures of cis / trans isomers. Rh I complexes of 1a , 3a , and bidentate 3h have also been synthesized.