Synthesis of Chiral 2,2'-Bis(diphenylphosphino)-1,1'-binaphthyl (BINAP) via a Novel Nickel-Catalyzed Phosphine Insertion

Cai, D.; Payack, Joseph F.; Bender, Dean R.; Hughes, David L.; Verhoeven, Thomas R.; Reider, Paul J.

doi:10.1021/jo00102a059

Cited by 222 publications

(103 citation statements)

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“…Removal of the methyl ether with BBr 3 and triflation of the resulting naphthol led to the formation of 22 in a 62 % yield over the 2 steps. The final step in the ligand synthesis was the nickel-catalyzed crosscoupling between the triflate 22 and diphenylphosphane in the presence of NiCl 2 (dppe)/DABCO following the protocol of Cai [11] which gave the desired phosphne 6 in a low yield of 33 % (Scheme 3).…”

Section: Synthesis and Resolution Ofmentioning

confidence: 99%

Synthesis and Post‐Resolution Modification of New Axially Chiral Ligands for Asymmetric Catalysis

2010

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The synthesis of four new members of the Quinazolinap series of ligands is described. Three of these ligands were prepared by post-resolution modification of the known ligand (R)-7-chloro-2-isopropyl-Quinazolinap, a new approach which offers an expedient route to a range of enantiopure ligands as it precludes the need for resolution of each ligand prepared. The remaining ligand, 7-chloro-2-methylQuinazolinap, was prepared in a seven-step synthetic sequence incorporating palladium-and nickel-catalyzed transformations as the key steps. A diastereomerically pure palla-

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Section: Synthesis and Resolution Ofmentioning

confidence: 99%

Synthesis and Post‐Resolution Modification of New Axially Chiral Ligands for Asymmetric Catalysis

2010

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“…However, double phosphination reactions have rarely been described and are performed starting from bis-triflate substrates. [10,22] Under the same reaction conditions, biphenyl and binaphthyl substrates exhibit different reactivities.…”

Section: Resultsmentioning

confidence: 99%

“…This approach was successfully applied for the first time to the synthesis of BINAP. [10] 3) The use of an already pre-existing biaryl scaffold, most frequently a 2,2'-dibromobiaryl, which is submitted to halogen/metal exchange followed by trapping with ClPPh 2 , as in the case of BIPHEMP. [3] Unfortunately, these strategies cannot be applied to the synthesis of less sterically demanding C 1 -symmetric triortho-substituted derivatives.…”

Section: Introductionmentioning

confidence: 99%

Catalytic Palladium Phosphination: Modular Synthesis of C₁‐Symmetric Biaryl‐Based Diphosphines

Bonnafoux

Gramage‐Doria

Colobert

et al. 2011

Chemistry A European J

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A new family of C(1)-symmetric bis(diphenylphosphino)biphenyls have been prepared starting from readily available ortho,ortho'-dihalobiphenyl precursors by a palladium-catalyzed C-P coupling reaction. This process does not require the use of an additional ligand. To date, the synthesis of such diphosphines, by reaction of an intermediate biphenyldiyl dianion with ClPPh(2), mainly afforded the undesired cyclic phosphafluorene derivative. So far, no synthetic pathway has been found to avoid this intramolecular reaction. Herein we report the first general and external-ligand-free palladium-catalyzed phosphination reaction that allows the synthesis of a wide variety of substituted ortho,ortho'-bis(diphenylphosphino)biphenyls. With the aim of illustrating the scope and efficiency of this methodology, we applied it to the establishment of a straightforward access to C(1)-symmetrical analogues of the most powerful ligands used in homogenous catalysis and extended it to more challenging substrates.

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“…Additionally, a group from Merck Process Research has reported this transformation using nickel catalysis. Cai et al 46 have developed a practical method for the conversion of dinaphthol to BINAP without racemization of the sensitive starting diphenol.…”

Section: Conversion Of Aromatic Amino Acids Into Phosphinesmentioning

confidence: 99%

Synthesis of phosphine containing amino acids: Utilization of peptide synthesis in ligand design

et al. 2005

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Combinatorial chemistry has recently burst on the scene as a valuable tool for the discovery of new drug candidates. The ability to synthesize hundreds of compounds for screening is a useful complement to rational drug design. There are many similarities between the design of new therapeutic agents and the development of new asymmetric ligands, the most important of which is the limitation of a rational design strategy. For this reason a program was begun that would allow the use of combinatorial technology in the development of new ligands for transition metal catalyzed asymmetric reactions. Because of the large number of catalytic reactions they are involved in the system was based around phosphine ligands. This paper reports the synthesis of phosphine derivatives of alanine, proline, and the aromatic amino acids tyrosine and hydroxyphenylglycine. Examples of the use of these amino acids in the synthesis of peptides possessing helical and beta-turn secondary structures are presented. Metal complexes of these peptide-based ligands are used in hydrogenation and alkylation reactions.

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Synthesis of Chiral 2,2'-Bis(diphenylphosphino)-1,1'-binaphthyl (BINAP) via a Novel Nickel-Catalyzed Phosphine Insertion

Cited by 222 publications

References 0 publications

Synthesis and Post‐Resolution Modification of New Axially Chiral Ligands for Asymmetric Catalysis

Synthesis and Post‐Resolution Modification of New Axially Chiral Ligands for Asymmetric Catalysis

Catalytic Palladium Phosphination: Modular Synthesis of C₁‐Symmetric Biaryl‐Based Diphosphines

Synthesis of phosphine containing amino acids: Utilization of peptide synthesis in ligand design

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Synthesis of Chiral 2,2'-Bis(diphenylphosphino)-1,1'-binaphthyl (BINAP) via a Novel Nickel-Catalyzed Phosphine Insertion

Cited by 222 publications

References 0 publications

Synthesis and Post‐Resolution Modification of New Axially Chiral Ligands for Asymmetric Catalysis

Synthesis and Post‐Resolution Modification of New Axially Chiral Ligands for Asymmetric Catalysis

Catalytic Palladium Phosphination: Modular Synthesis of C1‐Symmetric Biaryl‐Based Diphosphines

Synthesis of phosphine containing amino acids: Utilization of peptide synthesis in ligand design

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Catalytic Palladium Phosphination: Modular Synthesis of C₁‐Symmetric Biaryl‐Based Diphosphines