Chiral metal complexes. 4. Resolution of racemic tertiary phosphines with chiral palladium(II) complexes. The chemistry of diastereomeric phosphine palladium(II) species in solution

Tani, Kazuhide; Brown, Leo D.; Ahmed, Jamil; Ibers, James A.; Yokota, Masahiro; Nakamura, Akira; Otsuka, Sei

doi:10.1021/ja00466a020

Cited by 169 publications

(58 citation statements)

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“…23 Cyclometalations that are assisted by oxygen, arsenic, and selenium donors are also known, though they are much rarer. 149,150 Chirality has been incorporated, for example through asymmetric ligand synthesis, [426][427][428][429][430] 436 Monomers are also present in solvents like benzene at high temperatures.…”

Section: Scheme 108mentioning

confidence: 99%

Cyclometalation Using d-Block Transition Metals: Fundamental Aspects and Recent Trends

2009

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Section: Scheme 108mentioning

confidence: 99%

Cyclometalation Using d-Block Transition Metals: Fundamental Aspects and Recent Trends

2009

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“…90 % yield. The synthesis of 3 from the reaction between 1 and Na 2 [PdCl 4 ] has been previously reported, [17] but the two-step method reported herein represents an overall yield of Ͼ85 %, which is a significant improvement on that of the one reported earlier (65 %).…”

Section: The Crystal Structure Ofmentioning

confidence: 77%

Cyclometallated Palladium Diphosphane Compounds Derived from the Chiral Ligand (S)‐PhCH(Me)NMe₂. Michael Addition Reactions to the Vinylidene Double Bond

et al. 2011

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Treatment of (S)‐PhCH(Me)NMe2 (1) with palladium(II) acetate in toluene gave the dinuclear cyclometallated complex [Pd{(S)‐C6H4CH(Me)NMe2‐C2,N}(μ‐OAc)]2 (2), inwhich the ligand is bonded to the palladium atom through the nitrogen phenyl carbon atoms. The reaction of 2 with aqueous sodium chloride gave the chloro‐bridged complex 3. The reaction of 3 with (R,R)‐DIOP [(4R,5R)‐4,5‐bis(diphenylphosphanylmethyl)‐2,2‐dimethyl‐1,3‐dioxolane], in a complex/phosphane 1:1 molar ratio, gave [{Pd[(S)‐C6H4CH(Me)NMe2‐C2,N]Cl}2(μ‐(R,R)‐DIOP)] (4). The reaction of 3 with (Ph2P)2C=CH2 (vdpp) in a 1:2 molar ratio in the presence of NH4PF6 or NaClO4 afforded [Pd{(S)‐C6H4CH(Me)NMe2‐C2,N}{(Ph2P)2C=CH2‐P,P′}][Y] [Y = PF6– (5); Y = ClO4– (6), respectively]. The treatment of 5 with acetylacetone in the presence of anhydrous sodium carbonate or with methanol afforded the addition products, [Pd{(S)‐C6H4CH(Me)NMe2‐C2,N}{(Ph2P)2CHCH2R‐P,P′}][PF6] [R = CH(COMe)2 (7); R = OMe (8), respectively], in good yield. The treatment of 6 with methyl acetoacetate and anhydrous sodium carbonate afforded the addition derivative [Pd{(S)C6H4CH(Me)NMe2C2,N}{(Ph2P)2CHCH2CH‐(COMe)(COOMe)‐P,P′}][ClO4] (9). The NMR spectra of the addition products showed that some of the resonances were duplicated due to the existence of optical isomers. The X‐ray crystal structure of complexes 2, 5, and 7 were determined by single‐crystal X‐ray diffraction analysis.

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“…Treatment of the desired diastereomer with 1,2-bis-(diphenylphosphino)ethane then liberates the phosphine enantiomer [reaction (13) Use of 38 has been reported [reaction (14)] (184). The chiral phosphines 34 and 35 were each obtained in low yields by fractional crystallization.…”

Section: + 29mentioning

confidence: 99%

Preparation of the Enantiomers of Compounds Containing Chiral Phosphorus Centers

Valentine

1984

Asymmetric Synthesis

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Chiral metal complexes. 4. Resolution of racemic tertiary phosphines with chiral palladium(II) complexes. The chemistry of diastereomeric phosphine palladium(II) species in solution

Cited by 169 publications

References 3 publications

Cyclometalation Using d-Block Transition Metals: Fundamental Aspects and Recent Trends

Cyclometalation Using d-Block Transition Metals: Fundamental Aspects and Recent Trends

Cyclometallated Palladium Diphosphane Compounds Derived from the Chiral Ligand (S)‐PhCH(Me)NMe₂. Michael Addition Reactions to the Vinylidene Double Bond

Preparation of the Enantiomers of Compounds Containing Chiral Phosphorus Centers

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Chiral metal complexes. 4. Resolution of racemic tertiary phosphines with chiral palladium(II) complexes. The chemistry of diastereomeric phosphine palladium(II) species in solution

Cited by 169 publications

References 3 publications

Cyclometalation Using d-Block Transition Metals: Fundamental Aspects and Recent Trends

Cyclometalation Using d-Block Transition Metals: Fundamental Aspects and Recent Trends

Cyclometallated Palladium Diphosphane Compounds Derived from the Chiral Ligand (S)‐PhCH(Me)NMe2. Michael Addition Reactions to the Vinylidene Double Bond

Preparation of the Enantiomers of Compounds Containing Chiral Phosphorus Centers

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Cyclometallated Palladium Diphosphane Compounds Derived from the Chiral Ligand (S)‐PhCH(Me)NMe₂. Michael Addition Reactions to the Vinylidene Double Bond