The first synthesis of chiral phosphinocarboxylic acid ligands, trans-2-(diphenylphosphino)cycloalkanecarboxylic acids. The phosphine-palladium complexes catalyzed asymmetric allylic alkylation

Okada, Yasukazu; Minami, Tōru; Sasaki, Y.; Umezu, Yasuo; Yamaguchi, Masahiko

doi:10.1016/s0040-4039(00)97502-6

Cited by 43 publications

(5 citation statements)

References 14 publications

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“…Our results must also be considered in a broader context. Of the several metal-promoted reactions that have been the subject of investigations in asymmetric synthesis, 2 palladium-catalyzed allylations 5, [24][25][26][27][28][29][30][31][32][35][36][37][38][39][40][41] have been under especially intense scrutiny. A large number of chiral ligands have been studied with great success in these reactions (Figure 17).…”

Section: Discussionmentioning

confidence: 99%

Molecular Mechanics Predictions and Experimental Testing of Asymmetric Palladium-Catalyzed Allylation Reactions Using New Chiral Phenanthroline Ligands

et al. 1996

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Molecular mechanics calculations were used to probe the conformational properties of a number of substituted phenanthrolines and their η3-allylpalladium complexes. Special attention was focused on phenanthrolines bearing chiral, terpene-derived, alkyl and alkenyl groups at C(2). Based upon these calculations, predictions could then be made regarding the suitability of the several ligands for use in asymmetric palladium-catalyzed substitution reactions of allylic acetates. Each of the substituted phenanthrolines was prepared by straightforward means. Use of these ligands in catalytic allylations gave results which were in good agreement with the calculation-based predictions. The highest levels of asymmetric induction were predicted and were obtained with a readily available 2-(2-bornyl)phenanthroline ligand 13. The results were compared with previously reported data obtained using other ligands. Overall, this work provides further indication of the potential utility of a combined calculational/experimental approach for the design of chiral catalysts.

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Section: Discussionmentioning

confidence: 99%

Molecular Mechanics Predictions and Experimental Testing of Asymmetric Palladium-Catalyzed Allylation Reactions Using New Chiral Phenanthroline Ligands

et al. 1996

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“…Alternative ligand scaffolds were developed by Minami and co-workers which comprised chiral cycloalkylphosphines bearing a carboxylic acid group on the ring or in the β-position. 86 , 87 These ligands were able to catalyze the addition of malonate or phosphonoacetate nucleophiles to allylic acetates. While similar in design, it was proposed that the ligand would act in an opposite fashion to the ligands designed by Kumada and Hayashi, with the carboxylate group exerting electronic repulsion onto the incoming, negatively charged nucleophile.…”

Section: Carbon–carbon Bond-forming Reactionsmentioning

confidence: 99%

“…This was followed in 1986 by Hayashi and co-workers, whereby chiral ferrocenylphosphine ligands were modified with hydroxyalkylamino groups that could hydrogen bond with the deprotonated malonate or alkyl isocyanide nucleophiles. , Enantioselectivities of up to 92% ee were obtained, suggesting that attractive NCIs were viable for achieving the highest levels of enantioinduction. Alternative ligand scaffolds were developed by Minami and co-workers which comprised chiral cycloalkylphosphines bearing a carboxylic acid group on the ring or in the β-position. , These ligands were able to catalyze the addition of malonate or phosphonoacetate nucleophiles to allylic acetates. While similar in design, it was proposed that the ligand would act in an opposite fashion to the ligands designed by Kumada and Hayashi, with the carboxylate group exerting electronic repulsion onto the incoming, negatively charged nucleophile.…”

Section: Carbon–carbon Bond-forming Reactionsmentioning

confidence: 99%

Recent Developments in Enantioselective Transition Metal Catalysis Featuring Attractive Noncovalent Interactions between Ligand and Substrate

et al. 2020

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Enantioselective transition metal catalysis is an area very much at the forefront of contemporary synthetic research. The development of processes that enable the efficient synthesis of enantiopure compounds is of unquestionable importance to chemists working within the many diverse fields of the central science. Traditional approaches to solving this challenge have typically relied on leveraging repulsive steric interactions between chiral ligands and substrates in order to raise the energy of one of the diastereomeric transition states over the other. By contrast, this Review examines an alternative tactic in which a set of attractive noncovalent interactions operating between transition metal ligands and substrates are used to control enantioselectivity. Examples where this creative approach has been successfully applied to render fundamental synthetic processes enantioselective are presented and discussed. In many of the cases examined, the ligand scaffold has been carefully designed to accommodate these attractive interactions, while in others, the importance of the critical interactions was only elucidated in subsequent computational and mechanistic studies. Through an exploration and discussion of recent reports encompassing a wide range of reaction classes, we hope to inspire synthetic chemists to continue to develop asymmetric transformations based on this powerful concept.

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“…While the present work was in progress, Pfaltz, Helmchen, and Williams have independently introduced P,N ligands capable of chelation of Pd between a traditionally arylated phosphorus atom and an imine-type nitrogen contained in an oxazoline ring ( 4 ); , analogues, containing other heteroatoms in lieu of the phosphorus (S, Se, O, or N), were reported subsequently. Several other types of ligands have more recently been reported to also exhibit high enantioselectivity in at least one if not more cases of allylic substitution. − …”

Section: Introductionmentioning

confidence: 99%

Derivatives of 2-Amino-2‘-diphenylphosphino-1,1‘-binaphthyl (MAP) and Their Application in Asymmetric Palladium(0)-Catalyzed Allylic Substitution

et al. 1998

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-036Derivatives of 2-Amino-2'-diphenylphosphino-1,1'-binaphthyl (MAP) and Their Application in Asymmetric Palladium(0)-Catalyzed Allylic Substitution.-The novel chiral biaryls (I), readily synthesized from the corresponding N-unsubstituted optically active precursor, are utilized as chiral ligands in the substitution reaction of allylic acetate (II) with in situ generated malonate-type nucleophiles. The substituents at the amino group of the ligand have only little effect on the enantioselectivity of the reaction, with the maximum of 73% e.e. attained in the case of ligand (Ib).

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The first synthesis of chiral phosphinocarboxylic acid ligands, trans-2-(diphenylphosphino)cycloalkanecarboxylic acids. The phosphine-palladium complexes catalyzed asymmetric allylic alkylation

Cited by 43 publications

References 14 publications

Molecular Mechanics Predictions and Experimental Testing of Asymmetric Palladium-Catalyzed Allylation Reactions Using New Chiral Phenanthroline Ligands

Molecular Mechanics Predictions and Experimental Testing of Asymmetric Palladium-Catalyzed Allylation Reactions Using New Chiral Phenanthroline Ligands

Recent Developments in Enantioselective Transition Metal Catalysis Featuring Attractive Noncovalent Interactions between Ligand and Substrate

Derivatives of 2-Amino-2‘-diphenylphosphino-1,1‘-binaphthyl (MAP) and Their Application in Asymmetric Palladium(0)-Catalyzed Allylic Substitution

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