Synthesis of Functional Tripodal Phosphines with Amino and Ether Groups by the Hydrophosphination of Trivinyl Ethers with Secondary Phosphines

Опарина, Л. А.; Гусарова, Н. К.; Vysotskaya, O. V.; Artem’ev, Alexander V.; Kolyvanov, Nikita A.; Трофимов, Б. А.

doi:10.1055/s-0033-1340497

Cited by 8 publications

(1 citation statement)

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“…Among them, the addition of P(X)–H (X = none, O, S or Se) to diverse alkenes is one of the most powerful and 100% atom-economic approaches to construct new C–P bonds, that provide straightforward access to tertiary phosphines and their chalcogenides [8–12]. Conventionally, the activation of the P–H bonds in this reaction is achieved by using radical initiators [13–15], Brønsted/Lewis acids [16–17] and bases [18–20] as well as transition metal catalysts [21–23]. Also, examples of the microwave-assisted [24–25] and photoinduced [26] addition are described.…”

Section: Resultsmentioning

confidence: 99%

Aerobic addition of secondary phosphine oxides to vinyl sulfides: a shortcut to 1-hydroxy-2-(organosulfanyl)ethyl(diorganyl)phosphine oxides

Малышева¹,

Artem’ev²,

Гусарова³

et al. 2015

Beilstein J. Org. Chem.

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Section: Resultsmentioning

confidence: 99%

Aerobic addition of secondary phosphine oxides to vinyl sulfides: a shortcut to 1-hydroxy-2-(organosulfanyl)ethyl(diorganyl)phosphine oxides

Малышева¹,

Artem’ev²,

Гусарова³

et al. 2015

Beilstein J. Org. Chem.

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Ca^II, Yb^II and Sm^II Bis(Amido) Complexes Coordinated by NHC Ligands: Efficient Catalysts for Highly Regio‐ and Chemoselective Consecutive Hydrophosphinations with PH₃

Lapshin

Basalov

Lyssenko

et al. 2018

Chemistry A European J

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The first example of intermolecular hydrophosphination of styrene,2 -vinylpyridine and phenylacetylene with PH 3 catalyzed by bis-(amido) complexes [(Me 3 Si) 2 N] 2 M(NHC) 2 (M = Ca, Yb, Sm) coordinated by NHC ligands is described. The reactions of styrene with PH 3 proceed under mild conditions in quantitative yields to afford only anti-Markovnikov product and allow for the chemoselective synthesis of primary,s econdary and tertiary phosphines. Addition of phenylacetylene to PH 3 regardless the initial molar substrates ratio resultsi nt he exclusive formation of at ertiaryt ris-(Z-styryl)-phosphine. Crucial effect of the Lewis base coordinated to the metal ion in precatalyst on catalytic activity in styrene hydrophosphinationw ith PH 3 was demonstrated. Free NHCs were also found to be able to promote addition of PH 3 to styrene, however they provide much lower reactionr ates comparedt ot he metal complexes.The formation of CÀPb onds by single-step intermolecular hydrophosphination reactions of unsaturated substrates is a promising, atom-efficient route to av ariety of phosphorus-containing compounds. To date, an umber of examples of this transformationh ave been achieved due to acid, [1] base, [2] dtransition, [3] alkaline-earth, [4] andr are-earth metal catalysis. [4a, 5] Radicali nitiation [2a,c, 6] was also reported and is covered in several reviews. [2c, 5e, 7] Despite the progress achieved in this area, a substrate scope of this reactionr emains limited and mainly involves activated olefins and ubiquitousp henyl-and diphenylphosphine. Meanwhile, PH 3 addition to alkenes and alkynes, which is ap rogressive and convenient syntheticr oute to av ariety of primary,s econdary and tertiaryp hosphines, still re-mains poorly explored. Ease of synthesis of PH 3 ,i ts low cost (vs. PhPH 2 )a nd availability make it ac ommercially attractive startingc ompound fort he synthesis of phosphines. Hydrophosphination of multiple CÀCb onds with PH 3 becomes feasible under free radical initiation, [8] acid [1] and superbasic [9] conditions, or UV irradiation. [10] However,t his reaction suffers from a lack of selectivity.T he only example of applying late transition metal complexes for catalytic hydrophosphination of activated substrates (acrylonitrile, [11] ethyl acrylate, [12] formaldehyde [13] ) with PH 3 was published by Pringle and co-workers. No examples of PH 3 addition to non-activated olefins, vinyl arenes and alkynes catalyzed by rare-and alkaline-earth metals complexes have been published so far.M oreover,t he examples of hydrophosphination reactions catalyzed by free carbenes also still remain unknown despite the immense progress in organocatalysis achieved through their use. [14] We found that homoand heterolepticY b II ,S m II and Ca II amido complexes [4a,c, 5b] performing with high catalytic activity in styrene hydrophosphination with Ph 2 PH and PhPH 2 proved to be completely inert in the case of PH 3 .C omplex {LO NO4 }YbN(SiMe 3 ) 2 (1) [4a] was the only exception that enabled transformationo fP H 3...

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New (aminomethyl)phosphines via selective hydrophosphination and/or phosphorus based Mannich condensation reactions

Cao

Elsegood

Lastra-Calvo

et al. 2017

Journal of Organometallic Chemistry

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Controlled stepwise reaction of a geminal substituted alkene or primary amine group afforded a small library of new functionalised tertiary and ditertiary phosphines. Accordingly, Mannich based condensation of the commercially available disubstituted arene C 6 H 4 (NH 2){2-C(Me)=CH 2 } with HOCH 2 PR 2 (R 2 = Cg: 1,3,5,7-tetramethyl-2,4,8-trioxa-6phosphaadamantyl; Ph 2) afforded the (aminomethyl)phosphines C 6 H 4 (NHCH 2 PCg){2-C(Me)=CH 2 } L 1 and C 6 H 4 (NHCH 2 PPh 2){2-C(Me)=CH 2 } L 2 in approx. 60% yield. In addition to the formation of L 2 , the diphosphine L 3 was also identified and independently synthesised upon reaction of C 6 H 4 (NH 2){2-C(Me)=CH 2 } with two equiv. of HOCH 2 PPh 2 in CH 3 OH under reflux. Alternatively, reaction of C 6 H 4 (NH 2){2-C(Me)=CH 2 } with H-PR 2 (R 2 = Cg or Ph 2) in the presence of AIBN [2,2`-azobis(2-methylpropionitrile)] as free radical initiator, afforded the primary amine functionalised phosphines C 6 H 4 (NH 2){2-CH(Me)CH 2 PCg} L 4 and C 6 H 4 (NH 2){2-CH(Me)CH 2 PPh 2 } L 5 in 85% and 66% isolated yields respectively. In both cases only the anti-Markovnikov addition products were observed. Subsequent reaction of L 5 with HOCH 2 PR 2 (R 2 = Ph 2) afforded the unsymmetrical ditertiary phosphine C 6 H 4 (NHCH 2 PPh 2){2-CH(Me)CH 2 PPh 2 } L 6. Some preliminary coordination studies towards [RuCl(µ-Cl)(η 6-C 10 Η 14)] 2, [AuCl(tht)] (tht = tetrahydrothiophene) and [MCl 2 (η 4-cod)] (M = Pd, Pt; cod = cycloocta-1,5-diene) demonstrate these new ligands behave as classic P-donors leaving the pendant amino or alkenyl groups non-coordinating. All compounds have been characterised by multinuclear NMR, FT−IR, mass spectrometry and microanalysis. Single crystal X-ray studies have been performed on L 3 , L 5 , L 6 , 1, 3b•0.5CH 2 Cl 2 , 4a•1.5CH 2 Cl 2 , 5 and 6•0.5CDCl 3 •0.5C 4 H 10 O

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Synthesis of Functional Tripodal Phosphines with Amino and Ether Groups by the Hydrophosphination of Trivinyl Ethers with Secondary Phosphines

Cited by 8 publications

References 8 publications

Aerobic addition of secondary phosphine oxides to vinyl sulfides: a shortcut to 1-hydroxy-2-(organosulfanyl)ethyl(diorganyl)phosphine oxides

Aerobic addition of secondary phosphine oxides to vinyl sulfides: a shortcut to 1-hydroxy-2-(organosulfanyl)ethyl(diorganyl)phosphine oxides

Ca^II, Yb^II and Sm^II Bis(Amido) Complexes Coordinated by NHC Ligands: Efficient Catalysts for Highly Regio‐ and Chemoselective Consecutive Hydrophosphinations with PH₃

New (aminomethyl)phosphines via selective hydrophosphination and/or phosphorus based Mannich condensation reactions

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Synthesis of Functional Tripodal Phosphines with Amino and Ether Groups by the Hydrophosphination of Trivinyl Ethers with Secondary Phosphines

Cited by 8 publications

References 8 publications

Aerobic addition of secondary phosphine oxides to vinyl sulfides: a shortcut to 1-hydroxy-2-(organosulfanyl)ethyl(diorganyl)phosphine oxides

Aerobic addition of secondary phosphine oxides to vinyl sulfides: a shortcut to 1-hydroxy-2-(organosulfanyl)ethyl(diorganyl)phosphine oxides

CaII, YbII and SmII Bis(Amido) Complexes Coordinated by NHC Ligands: Efficient Catalysts for Highly Regio‐ and Chemoselective Consecutive Hydrophosphinations with PH3

New (aminomethyl)phosphines via selective hydrophosphination and/or phosphorus based Mannich condensation reactions

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Ca^II, Yb^II and Sm^II Bis(Amido) Complexes Coordinated by NHC Ligands: Efficient Catalysts for Highly Regio‐ and Chemoselective Consecutive Hydrophosphinations with PH₃