Halide-bridged tetranuclear organocopper(<scp>i</scp>) clusters supported by indolyl-based <i>NCN</i> pincer ligands and their catalytic activities towards the hydrophosphination of alkenes

Yuan, Qingbing; Huang, Zeming; Wu, Weikang; Hong, Dongjing; Zhu, Shan; Wei, Jieding; Zhou, Shuangliu; Wang, Shaowu

doi:10.1039/d2dt02654f

Cited by 5 publications

(2 citation statements)

References 73 publications

(102 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The copper(I) compound [(PPh 3 )CuH] 6 , which is a precursor to (PPh 3 )CuPPh 2 upon treatment with Ph 2 PH, is also an effective precatalyst. Prior study of copper compounds in hydrophosphination catalysis is consistent with these observations, ,,,,− , but the observation of successful hydrophosphination of unactivated alkenes with 1 is unique among that series and related to photocatalytic conditions. That reactivity indicates that the operant mechanism of P–C bond formation is migratory insertion.…”

Section: Introductionsupporting

confidence: 54%

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

et al. 2022

View full text Add to dashboard Cite

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.

show abstract

Section: Introductionsupporting

confidence: 54%

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

et al. 2022

View full text Add to dashboard Cite

show abstract

“…38 Solution behavior of 1 under these conditions is consistent with [(Ph2PH)CuPPh2]n. The copper(I) compound [(PPh3)CuH]6, 38 which is a precursor to (PPh3)CuPPh2 upon treatment with Ph2PH, 39 was also an effective precatalyst. Prior study of copper compounds in hydrophosphination catalysis are consistent with these observations, 16,25,26,38,[40][41][42][43][44][45][46][47] but the observation of successful hydrophosphination of unactivated alkenes with 1 is unique among that series and tied to photocatalytic conditions. That reactivity indicates that the operant mechanism of P-C bond formation is migratory insertion.…”

Section: Introductionmentioning

confidence: 96%

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

Dannenberg

Seth

Finfer

et al. 2022

Preprint

View full text Add to dashboard Cite

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 the catalysis, and to provide direction for further study. A divergent Hammett plot indicates differing mechanisms based on electron density at the alkene substrate. A radical process was eliminated based on trapping reactions and in-situ EPR experiments. Isotopic labeling experiments, a zwitterionic trapping experiment, stoichiometric model reactions, and catalytic reactions using proxy intermediates indicate that both 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 (LMCT) 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 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.

show abstract

Earth Abundant Transition Metal Catalysts: New and Efficient Tools for Hydrophosphination and Oxyphosphination of Alkenes and Alkynes

Yuan,

Darcel

2024

ChemCatChem

View full text Add to dashboard Cite

Hydrophosphination and oxyphosphination are two important topical reactions in order to prepare organophosphorus derivatives from unsaturated derivatives such as alkenes and alkynes in a more sustainable fashion. Noticeably, metal catalysed versions have shown great interest and efficiency. By contrast, the use of earth abundant transition metal based catalysts for such transformations is less reported, even if there is a growing interest during the last decade. This review article reports and highlights recent developments using manganese, iron, cobalt, nickel and copper based catalysts for hydro‐ and oxyphosphination, notably exhibiting the selectivity, functional group tolerance, milder conditions and catalyst design. Even if significant progresses were made, the scopes are still rather limited (mainly focused on activated olefins such as styrenes) and chemo‐ and stereo‐selectivity issues still have to be solved, notably for asymmetric transformations. Of interest, the use of visible light including blue one as activator emerged giving promising and stimulating results at ambient conditions.

show abstract

Halide-bridged tetranuclear organocopper(i) clusters supported by indolyl-based NCN pincer ligands and their catalytic activities towards the hydrophosphination of alkenes

Abstract: The novel tetranuclear organocopper(I) clusters bridged by two halides and two indolyl-based NCN pincer ligands were synthesized through the reactions of Cu(I) halides with the lithiated ligands. Single-crystal X-ray diffraction...

Cited by 5 publications

References 73 publications

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

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

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

Earth Abundant Transition Metal Catalysts: New and Efficient Tools for Hydrophosphination and Oxyphosphination of Alkenes and Alkynes

Contact Info

Product

Resources

About