Catalyst-free hydrophosphination of alkenes in presence of 2-methyltetrahydrofuran: a green and easy access to a wide range of tertiary phosphines

Bissessar, Damien; Egly, Julien; Achard, Thierry; Steffanut, Pascal; Bellemin‐Laponnaz, Stéphane

doi:10.1039/c9ra04896k

Cited by 22 publications

(8 citation statements)

References 59 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Complexes 2 and 3 were evaluated as precatalysts for the hydrophosphination of p -divinylbenzene with Ph 2 PH and PhPH 2 (Scheme ). The use of diolefinic substrates such as p -divinylbenzene makes it possible to greatly expand the scope of catalytic hydrophosphination; however, this area remains poorly studied to date. ,, The high selectivities of the addition of phosphines to double bonds of p -divinylbenzene provided by precatalysts 2 and 3 allow for obtaining various phosphine products ( 5a – 5d ) depending on the initial substrates’ ratio (Table ). Similarly to the previous examples, the additions of PhPH 2 and Ph 2 PH to double bonds of p -divinylbenzene proceeded at high rates and conversions at room temperature.…”

Section: Hydrofunctionalization Catalysismentioning

confidence: 99%

Heteroleptic Bis(amido) Ca(II) and Yb(II) NHC Pincer Complexes: Synthesis, Characterization, and Catalytic Activity in Intermolecular Hydrofunctionalization of C═C Bonds

Lapshin

Cherkasov

2023

Organometallics

View full text Add to dashboard Cite

The treatment of 4,5-dimethyl-1,3-bis(2-pyridylmethyl)-1H-imidazolium chloride with M[N(SiMe 3 ) 2 ] 2 (THF) 2 (M = Ca, Yb) in 1:2 molar ratio results in the formation of a carbene fragment, activation of the picolyl CH bond, and dearomatization of one of the pyridine rings and affords bis(amido) complexes [(NHC)MN-(SiMe 3 ) 2 ] 2 (M = Ca (2), Yb (3)) coordinated by a μ 2 -bridging pincer NHC amido ligand. Complexes 2 and 3 demonstrate high catalytic activity and excellent regio-and chemoselectivities in the intermolecular hydrophosphination of styrene with both primary and secondary phosphines. Complexes 2 and 3 enable selective addition of PhPH 2 , Ph 2 PH, (CH 2 ) 4 NH, and (CH 2 ) 5 NH to para-divinylbenzene with high conversions under mild conditions. Tandem hydrophosphination/hydroamination of para-divinylbenzene was also performed.

show abstract

Section: Hydrofunctionalization Catalysismentioning

confidence: 99%

Heteroleptic Bis(amido) Ca(II) and Yb(II) NHC Pincer Complexes: Synthesis, Characterization, and Catalytic Activity in Intermolecular Hydrofunctionalization of C═C Bonds

Lapshin

Cherkasov

2023

Organometallics

View full text Add to dashboard Cite

show abstract

“…Phosphines P1-P4 were synthesized in one-step procedure starting from diphenylphosphine, namely Ph2PH, and the corresponding alkene derivative (i.e. methyl vinyl ketone, ethyl acrylate, tert-butyl acrylate, itaconic acid methyl ester), according to our previously reported procedure [51]: they were prepared by addition of the corresponding alkene compounds on Ph2PH (1.2 equiv.) in presence of 2-MeTHF (4 equiv.)…”

Section: Synthesis Of the Phosphine Ligands P1-p4mentioning

confidence: 99%

Copper(I) complexes with remotely functionalized phosphine ligands: Synthesis, structural variety, photophysics and effect onto the optical properties

Egly

Bissessar

Achard

et al. 2021

Inorganica Chimica Acta

Self Cite

View full text Add to dashboard Cite

The synthesis, chemical and photophysical investigation of a series of eight novel copperhalide derivatives with different nuclearity is herein presented. One mononuclear copper(I) complex with formula [CuI(pyridine)(P)2], where P is a functionalized phosphine, six dinuclear derivatives bearing the rhombic {Cu2I2} subunits and with general formula [Cu(µ -I)(P)(N)]2 (N = pyridine, quinoline and 4-cyanopyridine) as well as one tetranuclear copperiodide clusters of general formula [Cu(µ -I)P]4 consisting of a cubane-like {Cu4X4} motif were straightforwardly prepared, also by means of mechano-chemical synthetic procedure.The phosphine ligands were prepared in excellent yield by using simple hydrophosphination reactions. For five of the investigated cuprous iodide derivatives their atom connectivity and solid-state crystalline packing was unambiguously confirmed by solving their single-crystal X-ray structure. All the investigated complexes resulted into photo-and thermally-stable luminescent species. In the solid state as microcrystalline powder samples, the complexes display intense photoluminescence ranging from the sky-blue to orange-red portion of the spectrum with PLQY values of 0.28-0.50 and 0.34-0.97 at room and low (77 K) temperature, respectively, depending on the nature of both the coordinated N-heteroaromatic ring and phosphine ligands. In spite of the remote location of the functionalization of the phosphine, profound effects are observed onto the solid-state emission properties highlighting the importance of microenvironment for the emitters in the aggregated phase.

show abstract

“…Hydrophosphination of styrene was examined first due to its common use in recent studies. 41,42,43,44 A chloroform-d1 solution of styrene was treated with 2 equiv. of phenylphosphine in the presence of 5 mol % of 1.…”

Section: Optimization Of Conditionsmentioning

confidence: 99%

Photocatalytic Hydrophosphination with Air-Stable and Commercially Available Bis(acetylacetonato)copper(II) (Cu(acac)2)

Dannenberg¹,

Waterman

2020

Preprint

View full text Add to dashboard Cite

Bis(acetylacetonato)copper(II) (Cu(acac)2, 1), is active for the hydrophosphination of alkenes and alkynes with primary and secondary phosphines. Under thermal conditions, the activity of 1 is comparable to some of the best literature catalysts, but 1 is unique in that set possessing air- and water-stability. However, under ambient temperature irradiation centered at 360 nm, the conversions are remarkable with some reactions complete in minutes and several rarely reported unactivated substrates achieving high conversions within hours. The photocatalytic conditions are critical, and comparison to literature catalysts has been made in which 1 demonstrates superior activity. Initial mechanistic work does not suggest a radical mechanism rather the formation of a copper(I) active species. Hammett analysis indicates that depending on the substrate, either a nucleophilic or insertion-based mechanism may be at work. The enhanced reactivity provided by light also appears to be generalizable to other copper(I) compounds under irradiation, representing a broader phenomenon in metal catalyzed P–C bond formation. This simple, bench-stable, and inexpensive catalyst is highly effective, placing hydrophosphination in the hands of many more synthetic chemists.

show abstract

Catalyst-free hydrophosphination of alkenes in presence of 2-methyltetrahydrofuran: a green and easy access to a wide range of tertiary phosphines

Abstract: A hydrophosphination reaction that is free of base, acid and catalyst, using only 2-methyltetrahydrofuran as additive has been performed.

Cited by 22 publications

References 59 publications

Heteroleptic Bis(amido) Ca(II) and Yb(II) NHC Pincer Complexes: Synthesis, Characterization, and Catalytic Activity in Intermolecular Hydrofunctionalization of C═C Bonds

Heteroleptic Bis(amido) Ca(II) and Yb(II) NHC Pincer Complexes: Synthesis, Characterization, and Catalytic Activity in Intermolecular Hydrofunctionalization of C═C Bonds

Copper(I) complexes with remotely functionalized phosphine ligands: Synthesis, structural variety, photophysics and effect onto the optical properties

Photocatalytic Hydrophosphination with Air-Stable and Commercially Available Bis(acetylacetonato)copper(II) (Cu(acac)2)

Contact Info

Product

Resources

About