Catalyst- and solvent-free hydrophosphination and multicomponent hydrothiophosphination of alkenes and alkynes

Moglie, Yanina; González-Soria, María José; Martín-García, Iris; Radivoy, Gabriel; Alonso, Francisco

doi:10.1039/c6gc00903d

Cited by 77 publications

(48 citation statements)

References 91 publications

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“…Exclusive formation of the Z ‐isomer of the anti‐Markovnikoff product indicates that the addition of H‐PPh 2 to the alkyne proceeds with trans selectivity. Although it was recently shown that hydrophosphination of PhC≡CH with HPPh 2 may proceed without a solvent or catalyst (70 °C, 16 h, 80 % conversion), we could not reproduce these results. As we use very dry conditions and distilled substrates, a small amount of water may be necessary.…”

Section: Resultsmentioning

confidence: 64%

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Complexation and Versatile Reactivity of a Highly Lewis Acidic Cationic Mg Complex with Alkynes and Phosphines

Pahl

Stennett

Volland

et al. 2019

Chemistry A European J

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[(BDI)Mg+][B(C6F5)4−] (1; BDI=CH[C(CH3)NDipp]2; Dipp=2,6‐diisopropylphenyl) was prepared by reaction of (BDI)MgnPr with [Ph3C+][B(C6F5)4−]. Addition of 3‐hexyne gave [(BDI)Mg+⋅(EtC≡CEt)][B(C6F5)4−]. Single‐crystal X‐ray analysis, NMR investigations, Raman spectra, and DFT calculations indicate a significant Mg‐alkyne interaction. Addition of the terminal alkynes PhC≡CH or Me3SiC≡CH led to alkyne deprotonation by the BDI ligand to give [(BDI‐H)Mg+(C≡CPh)]2⋅2 [B(C6F5)4−] (2, 70 %) and [(BDI‐H)Mg+(C≡CSiMe3)]2⋅2 [B(C6F5)4−] (3, 63 %). Addition of internal alkynes PhC≡CPh or PhC≡CMe led to [4+2] cycloadditions with the BDI ligand to give {Mg+C(Ph)=C(Ph)C[C(Me)=NDipp]2}2⋅ 2 [B(C6F5)4−] (4, 53 %) and {Mg+C(Ph)=C(Me)C[C(Me)=NDipp]2}2⋅2 [B(C6F5)4−] (5, 73 %), in which the Mg center is N,N,C‐chelated. The (BDI)Mg+ cation can be viewed as an intramolecular frustrated Lewis pair (FLP) with a Lewis acidic site (Mg) and a Lewis (or Brønsted) basic site (BDI). Reaction of [(BDI)Mg+][B(C6F5)4−] (1) with a range of phosphines varying in bulk and donor strength generated [(BDI)Mg+⋅PPh3][B(C6F5)4−] (6), [(BDI)Mg+⋅PCy3][B(C6F5)4−] (7), and [(BDI)Mg+⋅ PtBu3][B(C6F5)4−] (8). The bulkier phosphine PMes3 (Mes=mesityl) did not show any interaction. Combinations of [(BDI)Mg+][B(C6F5)4−] and phosphines did not result in addition to the triple bond in 3‐hexyne, but during the screening process it was discovered that the cationic magnesium complex catalyzes the hydrophosphination of PhC≡CH with HPPh2, for which an FLP‐type mechanism is tentatively proposed.

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Section: Resultsmentioning

confidence: 64%

“…As we use very dry conditions and distilled substrates, a small amount of water may be necessary. The product distribution in the reported catalyst‐free, thermally‐induced conversion is also different (100 % anti‐Markovnikoff, Z / E= 95:5) …”

Section: Resultsmentioning

confidence: 94%

Complexation and Versatile Reactivity of a Highly Lewis Acidic Cationic Mg Complex with Alkynes and Phosphines

Pahl

Stennett

Volland

et al. 2019

Chemistry A European J

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“…tional P À Hb onds, [1] 2-H-1,3,2-diazaphospholene 1a ( Figure 1) exhibits apeculiar hydridic propensity,asendowed by its unique diazaphospholene skeleton. [2] This unexpected PÀHb ond philicity leads to an inverted regioselectivity and opens new applications of phosphines in organic synthesis.…”

Section: Contrastingwiththewell-knownproticreactivityofconven-mentioning

confidence: 99%

A Nucleophilicity Scale for the Reactivity of Diazaphospholenium Hydrides: Structural Insights and Synthetic Applications

2019

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Nucleophilicity parameters (N,s N )o fagroup of representative diazaphospholenium hydrides were derived by kinetic investigations of their hydride transfer to as eries of reference electrophiles with knowne lectrophilicity (E) values, using the Mayrequation log k 2 = s N (N + E). The Nscale covers over ten Nunits,ranging from the most reactive hydride donor (N = 25.5) to the least of the scale (N = 13.5). This discloses the highest Nv alue ever quantified in terms of Mayrsn ucleophilicity scales reported for neutral transition-metal-free hydride donors and implies an exceptional reactivity of this reagent. Even the least reactive hydride donor of this series is still ab etter hydride donor than those of many other nucleophiles such as the C À H, B À H, Si À Ha nd transition-metal M À H hydride donors.S tructure-reactivity analysis reveals that the outstanding hydricity of 2-H-1,3,2-diazaphospholene benefits from the unsaturated skeleton.

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“…[59] Therefore, it is highly desirable to reduce the amount of catalyst (or avoid its use), and to minimize waste generatedd uring the reaction. [63][64][65][66][67][68][69][70][71][72] Important advantages of many of thesem ethods are their simplicity and efficiency.I np articular,r oom-temperature (RT) reactions are very attractive for potential further application.G iven all this, we focusedo nd eveloping the synthesis of organosilicon compoundsi nagreen chemistry manner. [63][64][65][66][67][68][69][70][71][72] Important advantages of many of thesem ethods are their simplicity and efficiency.I np articular,r oom-temperature (RT) reactions are very attractive for potential further application.G iven all this, we focusedo nd eveloping the synthesis of organosilicon compoundsi nagreen chemistry manner.…”

Section: Resultsmentioning

confidence: 99%

A Highly Effective Route to Si−O−Si Moieties through O‐Silylation of Silanols and Polyhedral Oligomeric Silsesquioxane Silanols with Disilazanes

Kuciński

Hreczycho

2019

ChemSusChem

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A simple and highly practical catalyst‐free O‐silylation of silanols with commercially available disilazanes has been developed under mild conditions. In the case of polyhedral oligomeric silsesquioxane (POSS) silanols and some other silanols, it was necessary to use catalytic amounts of inexpensive Bi(OTf)3 as additional catalyst. This efficient chlorine‐free protocol involves the synthesis of a wide range of important organosilicon derivatives such as unsymmetrical disiloxanes and functionalized silsesquioxanes.

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Catalyst- and solvent-free hydrophosphination and multicomponent hydrothiophosphination of alkenes and alkynes

Abstract: The hydrophosphination and hydrothiophosphination of alkenes and alkynes are accomplished in the absence of a solvent and a catalyst in a regio- and stereoselective manner.

Cited by 77 publications

References 91 publications

Complexation and Versatile Reactivity of a Highly Lewis Acidic Cationic Mg Complex with Alkynes and Phosphines

Complexation and Versatile Reactivity of a Highly Lewis Acidic Cationic Mg Complex with Alkynes and Phosphines

A Nucleophilicity Scale for the Reactivity of Diazaphospholenium Hydrides: Structural Insights and Synthetic Applications

A Highly Effective Route to Si−O−Si Moieties through O‐Silylation of Silanols and Polyhedral Oligomeric Silsesquioxane Silanols with Disilazanes

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