Cleavage of phosphorus-carbon bonds with sodium/naphthalene. Facile preparation of unsymmetrical diphosphines

Chou, Teh‐Chang; Tsao, Chung-Huang; Hung, Su Chun

doi:10.1016/0022-328x(86)80279-0

Cited by 24 publications

(4 citation statements)

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“…11 The incorporation of bromine was found to be 3.53 mmol g Ϫ1 (28.21%) by elemental analysis. Treatment of 1,2-bis(diphenylphosphino)ethane with a solution of the radical anion of naphthalene (preformed in situ from a mixture of naphthalene and sodium in tetrahydrofuran [THF]), 12 formed the corresponding phosphinyl species 6. The reaction of 6 with a slurry of the brominated poly(styrene-co-divinylbenzene) resin 5 afforded polymer-supported 1,2-bis(diphenylphosphino)ethane 7.…”

Section: Resultsmentioning

confidence: 99%

“…Diphenyl [2-(phenylphosphino)ethyl]phosphine, sodium salt 6 was prepared from sodium (3.33 g, 0.145 mol), naphthalene (15.5 g, 0.12 mol) and 1,2-bis(diphenylphosphino)ethane (1.7 g, 0.043 mol) according to Chou et al 12 Attachment of 6 to the poly(styrene-co-divinylbenzene) resin was performed via the method of Pitman and Hirao 19 using brominated poly(styreneco-divinylbenzene) resin 5 (4 g, 0.014 mol) to yield polymersupported 1,2-bis(diphenylphosphino)ethane 7 as brown coloured beads. δ P (162 MHz, CDCl 3 , gel-phase) Ϫ12.3 (br s).…”

Section: Synthesis Of Polymer-supported 12-bis(diphenylphosphino)ethanementioning

confidence: 99%

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Novel polymer-supported coupling/dehydrating reagents for use in organic synthesis

2004

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Two novel dehydrating reagents and, based on a phosphonium anhydride and an oxyphosphonium triflate respectively, were prepared by reaction of the corresponding polymer-supported phosphine oxides with triflic anhydride. Reagent, based on the novel phosphorus heterocycle 1,1,3,3-tetraphenyl-2-oxa-1,3-diphospholanium bis(trifluoromethanesulfonate), was found to be a useful reagent for ester and amide formation. A wide range of coupling/dehydration-type reactions, such as ester, amide, anhydride, peptide, ether and nitrile formation, were performed in high yield using the more readily prepared polymer-supported triphenylphosphine ditriflate, which was easily recovered and re-used several times without loss of efficiency. With primary alcohols, both reagents and provide an alternative to the Mitsunobu reaction, where the use of azodicarboxylates and chromatography to remove the phosphine oxide by-product can be avoided. The use of 4-dimethylaminopyridine allowed the esterification of secondary alcohols with to proceed in high yield but with retention of configuration.

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Section: Resultsmentioning

confidence: 99%

Section: Synthesis Of Polymer-supported 12-bis(diphenylphosphino)ethanementioning

confidence: 99%

Novel polymer-supported coupling/dehydrating reagents for use in organic synthesis

2004

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“…The three-step synthesis of diphosphine 1 is outlined in Scheme . A dark green solution of sodium naphthalide in THF was added to Ph 2 PCH 2 CH 2 PPh 2 (dppe) and the mixture left at room temperature until a dark red solution containing Na[Ph 2 PCH 2 CH 2 PPh] and NaPh had developed by P−C(Ph) bond cleavage . An excess of Me 3 SiCl was added, causing the immediate disappearance of the color as Ph 2 PCH 2 CH 2 PPhSiMe 3 , PhSiMe 3 , and NaCl were formed.…”

Section: Resultsmentioning

confidence: 99%

Intramolecular Dehydrofluorinative Coupling of the Asymmetric Diphosphine Ph₂PCH₂CH₂PPh(C₅F₄N-4) and Pentamethylcyclopentadienyl Ligands in a Rhodium Complex

2003

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The tetrafluoropyridyl-substituted diphosphine Ph 2 PCH 2 CH 2 PPh(C 5 F 4 N-4) (1) has been prepared in three steps from dppe. Comparison of the spectroscopic properties between trans-[RhCl(CO){PPh 2 (C 5 F 4 N-4)} 2 ] and analogous complexes of other fluorinated triaryl phosphines reveals the lower basicity of tetrafluoropyridylphosphines relative to pentafluorophenylphosphines. The reaction between [Cp*RhCl(µ-Cl)] 2 and 1 in the presence of [BF 4 -] yielded racemic diastereoisomers of [Cp*RhCl (1)] [BF 4 ]. In the S Rh R P and R Rh S P pair of enantiomers the Cp* and tetrafluoropyridyl groups have a cis disposition about the Rh-P bond, and in the S Rh S P and R Rh R P pair the groups are trans. In situ NMR experiments reveal that the cis pair, in which the Cp* and tetrafluoropyridyl groups are close, underwent rapid dehydrofluorinative C-C coupling to give the respective enantiomers of [{η 5 ,κP,κP-C 5 Me 4 CH 2 -2-C 5 F 3 N-4-PPhCH 2 -CH 2 PPh 2 }RhCl][BF 4 ] (6‚[BF 4 ]). The trans pair did not undergo coupling, but isomerized to the cis pair on heating in ethanol. The reaction between [Cp*RhCl(µ-Cl)] 2 and 1 in refluxing benzene afforded 6‚[BF 4 ] in 64% yield after anion metathesis. The structures of OPPh 2 -(C 5 F 4 N-4), the cis isomer of [Cp*RhCl(1)][BF 4 ], and one enantiomer of 6‚[BF 4 ], which crystallizes as a conglomerate, have been determined by single-crystal X-ray diffraction.

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“…Although 'anionic copper' was often prepared by the reaction of the lithium naphthalene radical anion with triorganophosphane adducts of copper(I) halides, [CuX(PR 3 )] n (X = Cl, Br, or I; R = phenyl or n-butyl) (Rieke et al, 1990), owing to the particularly good solubility in THF and accessibility of [CuCl(PCy 3 )] 2 (Cy = cyclohexyl) (Churchill & Rotella, 1979), this was the only copper precursor employed in our initial study reported herein. Also, we elected not to use triphenylphosphane (PPh 3 ) adducts of copper(I) halides due to the ease with which coordinated or free PPh 3 and mixed tertiary aryl-alkyl phosphanes undergo reductive cleavage of P-C(aryl) bonds, unlike trialkylphosphanes (Chou et al, 1986). Although reactions of [CuCl(PCy 3 )] 2 with four equivalents of MAn (M = Li, Na, or K) in THF appear by NMR spectra to afford similar products in solution, owing to the facile isolation and crystallization of the potassium salt, only the latter will be described now.…”

Section: Introductionmentioning

confidence: 99%

Crystal structure and synthesis of the bis(anthracene)dicuprate dianion as the dipotassium salt, [K(tetrahydrofuran)₂]₂[{Cu(9,10-η²-anthracene)}₂], the first anionic arene complex of copper

Young,

Brennessel,

Ellis

2023

Acta Crystallogr C

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Reactions of (tricyclohexylphosphane)copper(I) chloride with two equivalents of potassium anthracene (KAn) in tetrahydrofuran (THF) at 200 K provides air-sensitive but thermally stable (at 293 K) solutions from which yellow crystalline blocks of bis[bis(tetrahydrofuran-κO)potassium] bis(μ-anthracene-κ2 C 9:C 10)dicopper, [K(THF)2]2[{Cu(9,10-η2-C14H10)}2] or [K(C4H8O)2]2[Cu2(C14H10)2], 1, were isolated in about 50% yield. Single-crystal X-ray crystallographic analysis of 1 confirmed the presence of the first known (arene)cuprate. Also, unlike all previously known homoleptic (anthracene)metallates of d-block elements, which contain metals coordinated only to terminal rings, the organocuprate unit in 1 contains copper bound to the 9,10-carbons of the central ring of anthracene. No other d- or f-block metal is known to afford an anthracene or other aromatic hydrocarbon complex having the architecture of organodicuprate 1.

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Cleavage of phosphorus-carbon bonds with sodium/naphthalene. Facile preparation of unsymmetrical diphosphines

Cited by 24 publications

References 4 publications

Novel polymer-supported coupling/dehydrating reagents for use in organic synthesis

Novel polymer-supported coupling/dehydrating reagents for use in organic synthesis

Intramolecular Dehydrofluorinative Coupling of the Asymmetric Diphosphine Ph₂PCH₂CH₂PPh(C₅F₄N-4) and Pentamethylcyclopentadienyl Ligands in a Rhodium Complex

Crystal structure and synthesis of the bis(anthracene)dicuprate dianion as the dipotassium salt, [K(tetrahydrofuran)₂]₂[{Cu(9,10-η²-anthracene)}₂], the first anionic arene complex of copper

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Cleavage of phosphorus-carbon bonds with sodium/naphthalene. Facile preparation of unsymmetrical diphosphines

Cited by 24 publications

References 4 publications

Novel polymer-supported coupling/dehydrating reagents for use in organic synthesis

Novel polymer-supported coupling/dehydrating reagents for use in organic synthesis

Intramolecular Dehydrofluorinative Coupling of the Asymmetric Diphosphine Ph2PCH2CH2PPh(C5F4N-4) and Pentamethylcyclopentadienyl Ligands in a Rhodium Complex

Crystal structure and synthesis of the bis(anthracene)dicuprate dianion as the dipotassium salt, [K(tetrahydrofuran)2]2[{Cu(9,10-η2-anthracene)}2], the first anionic arene complex of copper

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Intramolecular Dehydrofluorinative Coupling of the Asymmetric Diphosphine Ph₂PCH₂CH₂PPh(C₅F₄N-4) and Pentamethylcyclopentadienyl Ligands in a Rhodium Complex

Crystal structure and synthesis of the bis(anthracene)dicuprate dianion as the dipotassium salt, [K(tetrahydrofuran)₂]₂[{Cu(9,10-η²-anthracene)}₂], the first anionic arene complex of copper