Application of a base-induced [1,2]-rearrangement to synthesize thiophosphonate bidentate S(sp2)–N monoanionic ligand: Characterization of its silver and palladium complexes

Marie, Sabrina; Lutz, Martin; Spek, Anthony L.; Gebbink, Robertus J. M. Klein; Koten, Gerard van; Kervarec, Nelly; Michaud, François; Salaün, Jean-Yves; Jaffrès, Paul‐Alain

doi:10.1016/j.jorganchem.2009.08.035

Cited by 12 publications

(6 citation statements)

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“…This rearrangement proceeds by an ortho-metallation that can be characterized at a low temperature [93]. Then, the o -lithium species rearranges to produce 2-hydroxyarylphosphonate [94].…”

Section: Reviewmentioning

confidence: 99%

“…Aryl dialkyl phosphate, which was readily obtained by the AT reaction from phenol as shown in Scheme 31 [ 91 ], can be employed for the production of aryl phosphonate by applying a phospho-Fries rearrangement (a rearrangement initially reported by Melvin et al [ 92 ]). This rearrangement proceeds by an ortho-metallation that can be characterized at a low temperature [ 93 ]. Then, the o -lithium species rearranges to produce 2-hydroxyarylphosphonate [ 94 ].…”

Section: Reviewmentioning

confidence: 99%

See 1 more Smart Citation

Atherton–Todd reaction: mechanism, scope and applications

Corre¹,

Berchel²,

Couthon‐Gourvès³

et al. 2014

Beilstein J. Org. Chem.

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146

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SummaryInitially, the Atherton–Todd (AT) reaction was applied for the synthesis of phosphoramidates by reacting dialkyl phosphite with a primary amine in the presence of carbon tetrachloride. These reaction conditions were subsequently modified with the aim to optimize them and the reaction was extended to different nucleophiles. The mechanism of this reaction led to controversial reports over the past years and is adequately discussed. We also present the scope of the AT reaction. Finally, we investigate the AT reaction by means of exemplary applications, which mainly concern three topics. First, we discuss the activation of a phenol group as a phosphate which allows for subsequent transformations such as cross coupling and reduction. Next, we examine the AT reaction applied to produce fire retardant compounds. In the last section, we investigate the use of the AT reaction for the production of compounds employed for biological applications. The selected examples to illustrate the applications of the Atherton–Todd reaction mainly cover the past 15 years.

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“…This rearrangement proceeds by an ortho-metallation that can be characterized at a low temperature [93]. Then, the o -lithium species rearranges to produce 2-hydroxyarylphosphonate [94].…”

Section: Reviewmentioning

confidence: 99%

Section: Reviewmentioning

confidence: 99%

Atherton–Todd reaction: mechanism, scope and applications

Corre¹,

Berchel²,

Couthon‐Gourvès³

et al. 2014

Beilstein J. Org. Chem.

Self Cite

146

View full text Add to dashboard Cite

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“…173 Air and moisture stable Ag(I) phosphine complexes containing a 2-thiophosphonate functionalised pyrrole, which act as S,N-chelate ligand, have been reported. 174 Gold(I) complexes with side-on coordinated alkynyls have been investigated. Mono-and di-meric gold complexes are stabilised by phosphines, nitrogen ligands or bridging halides.…”

Section: Phosphine Chalcogen and Related Ligandsmentioning

confidence: 99%

Silver and gold

Meyer¹,

Schuh²,

Mohr³

2010

Annu. Rep. Prog. Chem., Sect. A: Inorg. Chem.

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“…23 Besides OH and SH functionalities, ortho-NH substituents are also accessible by 1,2-N→C rearrangements to the αposition as it could be shown for pyrroles. 24,25 If the α-positions are blocked, then 1,3-26 or 1,5-migrations occurred. 27 The less stable N−P bond, compared to O−P or C−P units, readily allows 1,2-migrations in the presence of aldehydes, 28,29 aziridines, 30 oximes, 31 and even pyrroles.…”

Section: ■ Introductionmentioning

confidence: 99%

Reactivity of Ferrocenyl Phosphates Bearing (Hetero-)Aromatics and [3]Ferrocenophanes toward Anionic Phospho-Fries Rearrangements

2017

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The temperature-dependent behavior within anionic phospho-Fries rearrangements (apFr) of P(O)(OFc)(EAr) (Fc = Fe(η-CH)(η-CH); E = O; Ar = phenyl, naphthyls, (R)-BINOL, [3]ferrocenophanyl; E = N, 1H-pyrrolyl, 1H-indolyl, 9H-carbazolyl; n = 1-3) is reported. While Fc undergoes one, the Ph-based apFr depends on temperature. First, the aryls are lithiated and rearranged, followed by Fc and N-heterocycles. Addition of MeSO thus gave methylated Fc, contrary to non-organometallic aromatics giving mixtures of HO and MeO derivatives. The (R)-BINOL Fc phosphate gave Fc-rearranged phosphonate in 91% de. Exchanging O- with N-aliphatics prevented apFr, due to higher electron density at P. Also 1,2-N→C migrations were observed. X-ray analysis confirms 1D H bridge bonds for OH and NH derivatives. The differences in reactivity between N-aliphatic and N-aromatic phosphoramidates were verified by electrochemistry. The redox potentials revealed lower values for the electron-rich aliphatics, showing no apFr, preventing a nucleophilic attack at P after lithiation. Redox separations for multiple Fc molecules are based on electrostatic interactions.

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Application of a base-induced [1,2]-rearrangement to synthesize thiophosphonate bidentate S(sp2)–N monoanionic ligand: Characterization of its silver and palladium complexes

Cited by 12 publications

References 54 publications

Atherton–Todd reaction: mechanism, scope and applications

Atherton–Todd reaction: mechanism, scope and applications

Silver and gold

Reactivity of Ferrocenyl Phosphates Bearing (Hetero-)Aromatics and [3]Ferrocenophanes toward Anionic Phospho-Fries Rearrangements

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