Novel enantiopure non-C2-symmetric NCN-pincer palladium complexes with l-proline chiral auxiliaries: mer η3-N,C,N versus square planar η4-N,C,N,O coordination

New chiral NCN-pincer palladium complexes containing proline ester moieties as chiral auxiliaries have been synthesized. The parent ligands 2,6-bis{[(S)-2-(methoxycarbonyl)-1-pyrrolidinyl]methyl}-1-bromobenzene LMe and 2,6-bis{[(S)-2-(benzoxycarbonyl)-1-pyrrolidinyl]methyl}-1-bromobenzene LBn were prepared in a single synthetic step and were obtained enantiomerically pure. Neutral arylpalladium bromide complexes 1a and 1b, formed upon treatment of the respective ligands LMe and LBn with [Pd2(dba)3]·CHCl3, were isolated as mixtures of three stereoisomers (SNSNSCSC, RNSNSCSC and RNRNSCSC). The ratio of stereoisomers is approximately 1:1:0.6 in the case of methyl ester derivative 1a, whereas the bulkier benzyl ester derivative 1b predominantly forms the (SNSNSCSC)-stereoisomer. Upon abstraction of the bromide ion from unresolved mixtures of 1a and 1b, cationic complexes 2 and 3, respectively, form as single diastereoisomers in which one of the ester prolinate carbonyl groups is coordinated to palladium according to X-ray crystal structure determination. This coordination of a carbonyl group to the metal has a substantial influence on the stereochemistry and results in the formation of a single diastereoisomer, having the (RNRNSCSC)-configuration, regardless of the stereochemistry or ratio of stereoisomers of the starting bromide compound. The structures of compounds 2 and 3 were somewhat unexpected since formation of the corresponding cationic [Pd(NCN)(OH2)]+ complexes was anticipated. In preliminary tests of these cationic complexes as catalysts in the enantioselective aldol condensation of benzaldehyde with methyl isocyanoacetate, modest selectivities were observed.

Graphical abstractFigure optionsDownload full-size imageDownload as PowerPoint slide

2,6-Bis[[(S)-2-(methoxycarbonyl)-1-pyrrolidinyl]methyl]bromobenzeneC20H27BrN2O4[α]D21=-78.8 (c 1.0, CHCl3)Source of chirality: l-prolineAbsolute configuration: SC

2,6-Bis[[(S)-2-(benzyloxycarbonyl)-1-pyrrolidinyl]methyl]bromobenzeneC35H35BrN2O4[α]D21=-52.9 (c 1.0, CHCl3)Source of chirality: l-prolineAbsolute configuration: SC

2,6-Bis[[(S)-2-(methoxycarbonyl)-1-pyrrolidinyl]methyl]phenylpalladiumC20H27BrN2O4Pd[α]D21=-8.7 (c 1.0, CHCl3)Source of chirality: l-proline and coordination to the metalAbsolute configuration: SNSNSCSC, RNRNSCSC and RNSNSCSC

2,6-Bis[[(S)-2-(benzyloxycarbonyl)-1-pyrrolidinyl]methyl]phenylpalladiumC35H35BrN2O4Pd[α]D21=-88.6 (c 1.0, CHCl3)Source of chirality: l-proline and coordination to the metalAbsolute configuration: SNSNSCSC, RNRNSCSC and RNSNSCSC

2,6-Bis[[(S)-2-(methoxycarbonyl)-1-pyrrolidinyl]methyl]phenylpalladium tetraflouroborateC20H27N2O4PdBF4[α]D21=+42.7 (c 0.5, acetone)Source of chirality: l-proline and coordination to the metalAbsolute configuration: RNRNSCSC

2,6-Bis[[(S)-2-(methoxycarbonyl)-1-pyrrolidinyl]methyl]phenylpalladium hexafluorophosphateC20H27N2O4PdPF6[α]D21=+48.9 (c 0.5, acetone)Source of chirality: l-proline and coordination to the metalAbsolute configuration: RNRNSCSC

2,6-Bis[[(S)-2-(benzyloxycarbonyl)-1-pyrrolidinyl]methyl]phenylpalladium tetraflouroborateC32H35N2O4PdBF4[α]D21=+22 (c 0.5, acetone)Source of chirality: l-proline and coordination to the metalAbsolute configuration: RNRNSCSC

2,6-Bis[[(S)-2-(benzyloxycarbonyl)-1-pyrrolidinyl]methyl]phenylpalladium hexafluorophosphateC32H35N2O4PdPF6[α]D21=+56.4 (c 0.62, acetone)Source of chirality: l-proline and coordination to the metalAbsolute configuration: RNRNSCSC