Manganese(<scp>i</scp>)-catalyzed access to 1,2-bisphosphine ligands

Ge, Luo; Harutyunyan, Syuzanna R.

doi:10.1039/d1sc06694c

Cited by 37 publications

(19 citation statements)

References 66 publications

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“…The same group expanded the HP strategy toward α,β-unsaturated phosphine oxides to form a range of enantiopure 1,2-bisphosphine ligands. 77 2.3. Chemoselectivity.…”

Section: Stereoselectivity Product Distributions Due To Stereoselecti...mentioning

confidence: 99%

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Broken Promises? On the Continued Challenges Faced in Catalytic Hydrophosphination

2022

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In this Perspective, we discuss what we perceive to be the continued challenges faced in catalytic hydrophosphination chemistry. Currently the literature is dominated by catalysts, many of which are highly effective, that generate the same phosphorus architectures, e.g., anti-Markovnikov products from the reaction of activated alkenes and alkynes with diarylphosphines. We highlight the state of the art in stereoselective hydrophosphination and the scope and limitations of chemoselective hydrophosphination with primary phosphines and PH 3 . We also highlight the progress in the chemistry of the heavier homologues. In general, we have tried to emphasize what is missing from our hydrophosphination armament, with the aim of guiding future research targets.

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“…The same group expanded the HP strategy toward α,β-unsaturated phosphine oxides to form a range of enantiopure 1,2-bisphosphine ligands. 77 2.3. Chemoselectivity.…”

Section: Stereoselectivity Product Distributions Due To Stereoselecti...mentioning

confidence: 99%

“… Mechanistically, the authors suggested that the HP proceeded via metal–ligand cooperation, and the origin of the enantioselectivity was assessed by computational studies. The same group expanded the HP strategy toward α,β-unsaturated phosphine oxides to form a range of enantiopure 1,2-bisphosphine ligands …”

Section: Hydrophosphinationmentioning

confidence: 99%

Broken Promises? On the Continued Challenges Faced in Catalytic Hydrophosphination

2022

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“…Organophosphines are integral molecules in catalysis, synthetic chemistry, materials science, and more. − Metal-catalyzed hydrophosphination, the addition of a P–H bond across an unsaturated substrate, is one of the most promising and atom-economical P–C bond-forming reactions. − Progress has been made in expanding the available catalysts, scope, and selectivity of hydrophosphination in recent years. − However, limitations remain that hamper the synthetic utility of hydrophosphination. , Among the most notable limitations with known catalysts is that they often require special preparation and/or complex ancillary ligands and that most precatalysts are not air- and water-stable (i.e., not convenient). Known catalysts also have limitations in reactivity, often stymied by unactivated or highly substituted substrates, especially in intermolecular reactions. , …”

Section: Introductionmentioning

confidence: 99%

Divergent Mechanistic Pathways for Copper(I) Hydrophosphination Catalysis: Understanding That Allows for Diastereoselective Hydrophosphination of a Tri-substituted Styrene

et al. 2022

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Readily available and bench-stable Cu(acac) 2 (1) addresses many challenges in exploratory hydrophosphination catalysis. Mechanistic investigations were performed to answer questions that remain about the reactivity of 1, the role of light in catalysis, and to provide direction for further study. A divergent Hammett plot indicates different mechanisms based on electron density at the alkene substrate. A radical process was eliminated based on trapping reactions and in situ electron paramagnetic resonance experiments. Isotopic labeling experiments, a zwitterionic trapping experiment, stoichiometric model reactions, and catalytic reactions using proxy intermediates indicate that both the conjugate addition and insertion-based mechanistic pathways occur with this system, depending on the unsaturated substrate. Computational analysis indicates that the lowest energy transition is a ligand-to-metal charge transfer from the phosphido ligand where the LUMO has significant Cu−P antibonding character, suggesting that a weakened Cu−P bond accelerates insertion under photocatalytic conditions. This hypothesis explains the greater activity of 1 compared to prior copper-catalyzed hydrophosphination reports and appears to be a general phenomenon for copper(I) catalysts. These results have been leveraged to achieve heretofore unknown catalytic hydrophosphination reactivity, namely the diastereoselective hydrophosphination of a tri-substituted styrene substrate.

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“…The same catalyst was also viable to hydrophophinate α,β-unsaturated phosphine oxides with good to excellent ee (Scheme 124b). 505 The TON in the latter case is slightly lower than the former. Several reducible functionalities and heterocycles were well-tolerated by the corresponding alkyl phosphines.…”

Section: Manganese-catalyzed Hydroelementation Reactionsmentioning

confidence: 86%

Manganese-catalyzed hydrogenation, dehydrogenation, and hydroelementation reactions

et al. 2022

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Manganese(i)-catalyzed access to 1,2-bisphosphine ligands

Abstract: Chiral bisphosphine ligands are of key importance in transition-metal-catalyzed asymmetric synthesis of optically active products. However, the transition metals typically used are scarce and expensive noble metals, while the synthetic routes...

Cited by 37 publications

References 66 publications

Broken Promises? On the Continued Challenges Faced in Catalytic Hydrophosphination

Broken Promises? On the Continued Challenges Faced in Catalytic Hydrophosphination

Divergent Mechanistic Pathways for Copper(I) Hydrophosphination Catalysis: Understanding That Allows for Diastereoselective Hydrophosphination of a Tri-substituted Styrene

Manganese-catalyzed hydrogenation, dehydrogenation, and hydroelementation reactions

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