A practical synthesis of unsymmetrical triarylphosphines by heterogeneous palladium(0)-catalyzed cross-coupling of aryl iodides with diphenylphosphine

Xu, Zhaotao; Wang, Pingping; Chen, Qiurong; Cai, Mingzhong

doi:10.1016/j.jorganchem.2018.04.018

Cited by 7 publications

(2 citation statements)

References 66 publications

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“…31 P NMR (CDCl 3 , 121.5 MHz) δ – 5.7; 1 H NMR (CDCl 3 , 300 MHz) δ 7.18–7.35 (m, 4H), 7.26–7.37 (m, 15H); 13 C{ 1 H} NMR (CDCl 3 , 75.5 MHz) δ 128.6 (d, J = 7.0), 128.8, 133.9 (d, J = 19.5), 137.3 (d, J = 10.7); mp. 79–80 °C; all identical to those described in the literature. , …”

Section: Methodsmentioning

confidence: 99%

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Experimental and Theoretical Study on the “2,2′-Bipiridyl-Ni-Catalyzed” Hirao Reaction of >P(O)H Reagents and Halobenzenes: A Ni(0) → Ni(II) or a Ni(II) → Ni(IV) Mechanism?

2020

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It was found by us that the P–C coupling reaction of >P(O)H reagents with PhX (X = I and Br) in the presence of NiCl 2 /Zn as the precursors for the assumed Ni(0) complexant together with 2,2′-bipyridine as the ligand took place only with PhI at 50/70 °C. M06-2 X /6-31G(d,p)//PCM(MeCN) calculations for the reaction of Ph 2 P(O)H and PhX revealed a favorable energetics only for the loss of iodide following the oxidative addition of PhI on the Ni(0) atom. However, the assumed transition states with Ni(II) formed after P-ligand uptake and deprotonation could not undergo reductive elimination meaning a “dead-end route”. Hence, it was assumed that the initial complexation of the remaining Ni 2+ ions with 2,2′-bipyridine may move the P–C coupling forward via a Ni(II) → Ni(IV) transition. This route was also confirmed by calculations, and this mechanism was justified by preparative experiments carried out using NiCl 2 /bipyridine in the absence of Zn. Hence, the generally accepted Ni(0) → Ni(II) route was refuted by us, confirming the generality of the Ni(II) → N(IV) protocol, either in the presence of bipyridine, or using the excess of the >P(O)H reagent as the P -ligand. The results of the calculations on the complex forming ability of Ni(0) and Ni(II) with 2,2′-bipyridine or the P -reagents were in accord with our mechanistic proposition.

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Section: Methodsmentioning

confidence: 99%

“…79−80 °C; all identical to those described in the literature. 19,36 For the spectroscopic data of compounds 3a−c and 4, see the Supporting Information.…”

Section: ■ Introductionmentioning

confidence: 99%

Experimental and Theoretical Study on the “2,2′-Bipiridyl-Ni-Catalyzed” Hirao Reaction of >P(O)H Reagents and Halobenzenes: A Ni(0) → Ni(II) or a Ni(II) → Ni(IV) Mechanism?

2020

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

2019

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Nucleophilicity parameters (N, sN) of a group of representative diazaphospholenium hydrides were derived by kinetic investigations of their hydride transfer to a series of reference electrophiles with known electrophilicity (E) values, using the Mayr equation log k2=sN(N+E). The N scale covers over ten N units, ranging from the most reactive hydride donor (N=25.5) to the least of the scale (N=13.5). This discloses the highest N value ever quantified in terms of Mayr's nucleophilicity 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 a better hydride donor than those of many other nucleophiles such as the C−H, B−H, Si−H and transition‐metal M−H hydride donors. Structure–reactivity analysis reveals that the outstanding hydricity of 2‐H‐1,3,2‐diazaphospholene benefits from the unsaturated skeleton.

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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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A practical synthesis of unsymmetrical triarylphosphines by heterogeneous palladium(0)-catalyzed cross-coupling of aryl iodides with diphenylphosphine

Cited by 7 publications

References 66 publications

Experimental and Theoretical Study on the “2,2′-Bipiridyl-Ni-Catalyzed” Hirao Reaction of >P(O)H Reagents and Halobenzenes: A Ni(0) → Ni(II) or a Ni(II) → Ni(IV) Mechanism?

Experimental and Theoretical Study on the “2,2′-Bipiridyl-Ni-Catalyzed” Hirao Reaction of >P(O)H Reagents and Halobenzenes: A Ni(0) → Ni(II) or a Ni(II) → Ni(IV) Mechanism?

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

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

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