Asymmetric Synthesis of Chiral‐at‐P Alkenylphosphonamidates through Nickel‐Catalyzed C−P Coupling of Phosphoramidites and Alkenyl Halides

Chen, Xiaobing; Padín, Damián; Stindt, Charlotte N.; Feringa, Ben L.

doi:10.1002/anie.202307450

Cited by 13 publications

(4 citation statements)

References 103 publications

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“…This method relied on Ni(COD)(DQ) as precatalyst because the STM-BJ (scanning tunneling microscope break-junction) setup used by the authors is open to air. Other laboratories in academia and industry have opted to use Ni(COD)(DQ) due to the operational simplicity it provides, − and some have performed mechanistic studies to understand how ligand exchange occurs in the presence of ligand and substrate . With the commercialization of a majority of the precatalyst toolkit, we expect the findings enabled by the precatalysts to continue expanding.…”

Section: Air-stable Nickel(0) Precatalysts As Privileged Scaffolds In...mentioning

confidence: 99%

Benchtop Nickel Catalysis Invigorated by Electron-Deficient Diene Ligands

Rubel,

He,

Wisniewski

et al. 2024

Acc. Chem. Res.

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Metrics & MoreArticle Recommendations CONSPECTUS: Due to the rarity of precious metals like palladium, nickel catalysis is becoming an increasingly important player in organic synthesis, especially for the formation of bonds with sp 3 -hybridized carbon centers. Traditionally, catalytic processes involving active Ni( 0) species have relied on Ni(COD) 2 or in situ reduction of Ni(II) salts. However, Ni(COD) 2 is an air-and temperature-sensitive material that requires use in an inertatmosphere glovebox, and in situ reduction protocols of Ni(II) salts using metallic or organometallic reductants add additional complications to reaction development. This Account chronicles the development of air-stable Ni(0) precursors as replacements for Ni(COD) 2 or in situ reduction. Based on Schrauzer's seminal discovery of Ni(COD)(DQ) as an air-stable zerovalent organonickel complex, our research laboratories at Scripps Research and Bristol Myers Squibb have developed a class of precatalysts based on the Ni(COD)(EDD) (EDD = electron-deficient diene) framework, relying on the steric and electronic properties of the supporting diene to render the metal center stable to air, moisture, and even silica gel but reactive to ligand substitution and redox changes. The stable Ni(0) complexes can be accessed through ligand exchange with Ni(COD) 2 , through reduction of Ni(acac) 2 using DIBAL-H, or electrochemically via cathodic reduction of Ni(acac) 2 to Ni(COD) 2 , followed by addition of an EDD ligand in one pot. As a toolkit, the complexes demonstrate reactivity that is equivalent or enhanced compared to Ni(COD) 2 , catalyzing C−C and C−N cross-couplings, Miyaura borylations, C−H activations, and other transformations. Since the initial report on Ni(COD)(DQ), its reactivity in C(sp 2 )−CN activation, metallophotoredox, and electric field-induced cross-coupling have also been demonstrated. By incorporating the precatalyst toolkit into reaction discovery campaigns, our laboratories have been able to perform C(sp 3 )− S(alkyl) couplings and metallonitrenoid carboamination, both of which represent challenging transformations that were inaccessible with traditional phosphine, nitrogen, or electron-deficient olefin ligands. Computational and experimental studies demonstrate how the quinone ligands are hemilabile, adopting η 1 (O)-bound geometries to relieve steric strain or stabilize transition states and intermediates; redox-active, able to transiently oxidize the metal center; and electron-withdrawing or -donating, depending on metal oxidation state and coordination geometry. These studies show how the ligands enable key steps in catalysis beyond imparting airstability. Since our report documenting the catalytic activity of Ni(COD)(DQ), many other laboratories have also observed unique reactivity with this precatalyst. Ni(COD)(DQ) was found to offer superior reactivity to Ni(COD) 2 in C−N cross coupling to form N,N-diaryl sulfonamides and in preparation of biaryls from aryl halides and benzene through a Ni-mediated, base-assisted homolytic a...

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Section: Air-stable Nickel(0) Precatalysts As Privileged Scaffolds In...mentioning

confidence: 99%

Benchtop Nickel Catalysis Invigorated by Electron-Deficient Diene Ligands

Rubel,

He,

Wisniewski

et al. 2024

Acc. Chem. Res.

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“…[49] The same (R)-BINOLbased P(III) scaffolds also react with alkenyl halides when catalyzed by Ni(0) catalysts. Diastereomeric ratios of up to > 20 : 1 could be obtained with 10 mol % Ni(cod)(dq) [bis(1,5cyclooctadiene)(duroquinone) nickel(0)] in 1,2-dichloroethane at 80 °C after 12-24 h. [50] Palladium(II)-catalyzed approach towards P-chiral, enantiomerically enriched phosphinic hydrazones (R P )-88-S and (R P )-88-O was provided in 2020 by Pullarkat, Leung, and co-workers (Scheme 14, top). The PÀ NÀ N compounds constitute a class of important intermediates for the synthesis of diarylphosphinates such as (S P )-89, which can be obtained after acidic methanolysis of the phosphinic hydrazones with inversion of configuration.…”

Section: Synthesis By Palladium Catalysismentioning

confidence: 99%

“…The same ( R )‐BINOL‐based P(III) scaffolds also react with alkenyl halides when catalyzed by Ni(0) catalysts. Diastereomeric ratios of up to >20 : 1 could be obtained with 10 mol % Ni(cod)(dq) [bis(1,5‐cyclooctadiene)(duroquinone) nickel(0)] in 1,2‐dichloroethane at 80 °C after 12–24 h [50] …”

Section: Transition Metal‐catalyzed Approaches Towards P‐stereogenic ...mentioning

confidence: 99%

A Powerful P−N Connection: Preparative Approaches, Reactivity, and Applications of P‐Stereogenic Aminophosphines

Huber,

Bauer

2024

Chemistry A European J

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For more than five decades, P‐stereogenic aminophosphine chalcogenides and boranes have attracted scientific attention and are still in the focus of ongoing research. In the last years, novel transition metal‐based synthesis methods have been discovered, in addition to the long‐known use of chiral auxiliaries. Enantiomerically pure compounds with N–P+–X‐ (X = O, S, BH3) motifs served as valuable reactive building blocks to provide new classes of organophosphorus derivatives, thereby preserving the stereochemical information at the phosphorus atom. Over the years, intriguing applications in organocatalysis and transition metal catalysis have been reported for some representatives. Asymmetric reductions of C═C, C═N, and C═O double bonds were feasible with selected P‐stereogenic aminophosphine oxides in the presence of hydrogen transfer reagents. P‐stereogenic aminophosphine boranes could be easily deprotected and used as ligands for various transition metals to enable catalytic asymmetric hydrogenations of olefins and imines. This review traces the emergence of a synthetically and catalytically powerful functional compound class with phosphorus‐centered chirality in its main lines, starting from classical approaches to modern synthesis methods to current applications.

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“…From 2001 to 2023, a great number of P-stereogenic phosphorus ligands with structural diversity have been designed, synthesized, and applied in numerous catalytic asymmetric reactions. This remarkable advancement is largely ascribed to the development of many efficient methods for the synthesis of P-stereogenic organophosphorus compounds including novel chiral phosphorus ligands. − ,,,,− In addition, breakthrough results obtained by the use of P-stereogenic phosphorus ligands have encouraged researchers to devote their efforts to this area.…”

Section: A Historical Overview Of P-stereogenic Phosphorus Ligandsmentioning

confidence: 99%

P-Stereogenic Phosphorus Ligands in Asymmetric Catalysis

Imamoto

2024

Chem. Rev.

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Chiral phosphorus ligands play a crucial role in asymmetric catalysis for the efficient synthesis of useful optically active compounds. They are largely categorized into two classes: backbone chirality ligands and P-stereogenic phosphorus ligands. Most of the reported ligands belong to the former class. Privileged ones such as BINAP and DuPhos are frequently employed in a wide range of catalytic asymmetric transformations. In contrast, the latter class of P-stereogenic phosphorus ligands has remained a small family for many years mainly because of their synthetic difficulty. The late 1990s saw the emergence of novel P-stereogenic phosphorus ligands with their superior enantioinduction ability in Rh-catalyzed asymmetric hydrogenation reactions. Since then, numerous P-stereogenic phosphorus ligands have been synthesized and used in catalytic asymmetric reactions. This Review summarizes P-stereogenic phosphorus ligands reported thus far, including their stereochemical and electronic properties that afford high to excellent enantioselectivities. Examples of reactions that use this class of ligands are described together with their applications in the construction of key intermediates for the synthesis of optically active natural products and therapeutic agents. The literature covered dates back to 1968 up until December 2023, centering on studies published in the late 1990s and later years.

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Asymmetric Synthesis of Chiral‐at‐P Alkenylphosphonamidates through Nickel‐Catalyzed C−P Coupling of Phosphoramidites and Alkenyl Halides

Cited by 13 publications

References 103 publications

Benchtop Nickel Catalysis Invigorated by Electron-Deficient Diene Ligands

Benchtop Nickel Catalysis Invigorated by Electron-Deficient Diene Ligands

A Powerful P−N Connection: Preparative Approaches, Reactivity, and Applications of P‐Stereogenic Aminophosphines

P-Stereogenic Phosphorus Ligands in Asymmetric Catalysis

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