Nickel-catalysed diversification of phosphine ligands by formal substitution at phosphorus

Roediger, Sven; Leutenegger, Sebastian U; Morandi, Bill

doi:10.1039/d2sc02496a

Cited by 26 publications

(7 citation statements)

References 72 publications

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“…The deboration process of phosphine‐borane adduct 5 dg was also straightforward, and free phosphine 6 dg was produced in high yield in the presence of DABCO (Scheme 2c) [20] . Additionally, although pure free trivalent phosphines 6 db and 6 dc were not obtained in air, their corresponding HBF 4 salts 7 db and 7 dc were accessed from phosphine‐borane adducts in good yields (Scheme 2c) [17c, 21] . Such HBF 4 salts are air‐stable and can release free trivalent phosphines in situ by treatment with a base [22] …”

Section: Methodsmentioning

confidence: 99%

Csp³−P^III Bond Formation via Cross‐Coupling of Umpolung Carbonyls with Phosphine Halides Catalyzed by Nickel

Cheng

2023

Angew Chem Int Ed

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A novel method for the formation of Csp3−PIII bonds via the nickel‐catalyzed cross‐coupling of Umpolung carbonyls and phosphine chlorides is reported herein. This process leads to a series of alkylphosphines, which are characterized as sulfides or borane‐phosphine complexes after undergoing further transformation with moderate to good yields. Invaluable free alkylphosphines can be easily obtained by desulfurization or deboration of the products. A possible mechanistic pathway is also discussed. This report represents the first example of using renewable carbonyls as latent organometallic reagent surrogates for cross‐coupling with heteroatom electrophiles.

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Section: Methodsmentioning

confidence: 99%

Csp³−P^III Bond Formation via Cross‐Coupling of Umpolung Carbonyls with Phosphine Halides Catalyzed by Nickel

Cheng

2023

Angew Chem Int Ed

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“…(28)(29)(30)(31)(32) Our group has a longstanding interest in diverting the reactivity of phosphonium salts towards unusual transformations, such as C-P metathesis and related transformations for late-stage phosphine functionalization. (33,34) During our recent studies, (35) we discovered conditions under which the P-C(sp 3 ) bond of the phosphonium salt is activated in addition to the more reactive P-C(sp 2 ) bond if the phosphonium salt contained a tertiary alkyl group (Fig. 1C).…”

Section: Main Textmentioning

confidence: 99%

Frustrated Ion Pair-Enabled Cross-Electrophile Coupling of Unactivated Alkyl Electrophiles

Roediger

Boehm

Morandi

2023

Preprint

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Cross-electrophile coupling reactions have evolved into a major strategy for rapidly assembling important molecules, yet challenges remain for the formation of C(sp3)–C(sp3) bonds that form the core of nearly all organic compounds. Herein, we report a distinct, transition metal-free platform to form such bonds without the need for activating or stabilizing groups on the coupling partners. The reaction is enabled by an unusual single electron transfer in a frustrated ion pair and is complementary in terms of scope to transition metal-catalyzed processes. Moreover, we could further leverage this new mechanistic manifold in the design of other reactions, showing the broad potential of this new reactivity in organic synthesis.

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“…Therefore, the development of a reliable method to access stable 2-λ5-phosphaquinolines, especially the preparation of enantiomers, is in high demand (25)(26)(27)(28)(29)(30). Metal-catalyzed carbon-phosphorus coupling has emerged as an effective approach for achieving a diverse collection of phosphorus compounds (31)(32)(33)(34)(35)(36)(37)(38)(39). In 2017, Morandi and coworkers (40) reported an important breakthrough for palladiumcatalyzed C─P arylation of phosphines through metathesis pathway, enabling the convenient preparation of diverse triarylphosphines and phosphorus heterocycles (Fig.…”

Section: Introductionmentioning

confidence: 99%

Stereospecific nickel-catalyzed [4+2] heteroannulation of alkynes with aminophosphanes

et al. 2023

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Enantioenriched phosphorus compounds play crucial roles in many fields ranging from catalyst to materials science to drug development. Despite advances in the construction of phosphacycles, incorporation of a P-chirogenic center into heterocycles remains challenging. Here, we report an effective method for the preparation of phosphacycles through nickel-catalyzed [4+2] heteroannulation of internal alkynes with aminophosphanes derived from o -haloanilines. Notably, chiral 2-λ5-phosphaquinolines can be prepared from P-stereogenic substrates via NH/PH tautomeric equilibrium without loss of stereochemical integrity. The strategy is found to exhibit a broad scope in terms of both reaction components, enabling modular construction of libraries of 2-λ5-phosphaquinolines with different steric and electronic properties for fine-tuning photophysical properties, where some of these compounds showed distinct fluorescence with high quantum yields. A series of mechanistic studies further shed light on the pathway of the heteroannulation and reasons for stereospecificity.

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Nickel-catalysed diversification of phosphine ligands by formal substitution at phosphorus

Abstract: We report a diversification strategy for phosphines that enables the direct substituent exchange of tertiary phosphines. Alkylated phosphonium salts, prepared by standard alkylation of phosphines, are selectively dearylated in a...

Cited by 26 publications

References 72 publications

Csp³−P^III Bond Formation via Cross‐Coupling of Umpolung Carbonyls with Phosphine Halides Catalyzed by Nickel

Csp³−P^III Bond Formation via Cross‐Coupling of Umpolung Carbonyls with Phosphine Halides Catalyzed by Nickel

Frustrated Ion Pair-Enabled Cross-Electrophile Coupling of Unactivated Alkyl Electrophiles

Stereospecific nickel-catalyzed [4+2] heteroannulation of alkynes with aminophosphanes

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Nickel-catalysed diversification of phosphine ligands by formal substitution at phosphorus

Abstract: We report a diversification strategy for phosphines that enables the direct substituent exchange of tertiary phosphines. Alkylated phosphonium salts, prepared by standard alkylation of phosphines, are selectively dearylated in a...

Cited by 26 publications

References 72 publications

Csp3−PIII Bond Formation via Cross‐Coupling of Umpolung Carbonyls with Phosphine Halides Catalyzed by Nickel

Csp3−PIII Bond Formation via Cross‐Coupling of Umpolung Carbonyls with Phosphine Halides Catalyzed by Nickel

Frustrated Ion Pair-Enabled Cross-Electrophile Coupling of Unactivated Alkyl Electrophiles

Stereospecific nickel-catalyzed [4+2] heteroannulation of alkynes with aminophosphanes

Contact Info

Product

Resources

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Csp³−P^III Bond Formation via Cross‐Coupling of Umpolung Carbonyls with Phosphine Halides Catalyzed by Nickel

Csp³−P^III Bond Formation via Cross‐Coupling of Umpolung Carbonyls with Phosphine Halides Catalyzed by Nickel