A NEW EFFICIENT SYNTHESIS OF Ω-Aminoalkylidene-1,1-Bisphosphonate TETRAETHYLESTERS

Gourves, Jean‐Philippe; Couthon, Hélène; Sturtz, G.

doi:10.1080/10426509808036988

Cited by 19 publications

(14 citation statements)

References 12 publications

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“…1 H NMR spectra were obtained on Bruker DRX-500, DPX-400, and AM-250 spectrometers at 500.1, 400.1, and 250.1 MHz, respectively, and referenced to residual solvent protons. 13 C NMR spectra were obtained on Bruker DRX-500, DPX-400, and AM-250 spectrometers operating at 125.8, 100.6, and 62.9 MHz, respectively, and referenced to deuterated solvent signals. 11 B spectra were obtained on the Bruker DRX-500 spectrometer at 160.5 MHz and referenced externally to BF3‚OEt2 in C6D6 (δ ) 0.00 ppm).…”

Section: Methodsmentioning

confidence: 99%

“…An alternative procedure for the preparation of 22a has been recently reported by Sturtz and co-workers. 13 Ethyl esters 14g and 14h were converted into the sodium salts of the corresponding phosphonic and bisphosphonic acids, respectively, by treatment with excess bromotrimethylsilane (TMSBr) followed by the carbonate-buffered hydrolysis of the resulting trimethylsilyl esters and adjusting the pH of solutions to 11 with aqueous NaOH. 14 Ethyl esters 14g and 14h are the first examples of compounds containing both a closo-B 12 moiety and a phosphonate or bisphosphonate group, although similar compounds based on ortho-carborane have been reported.…”

Section: Synthesis Of Boronated Phosphonate and Gem-bisphosphonates B...mentioning

confidence: 99%

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S-Alkylation and S-Amination of Methyl Thioethers − Derivatives ofcloso-[B₁₂H₁₂]^2-. Synthesis of a Boronated Phosphonate,gem-Bisphosphonates, and Dodecaborane-ortho-carborane Oligomers

Kultyshev

Liu

et al. 2002

J. Am. Chem. Soc.

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A variety of S-alkylated products was prepared by alkylation of methyl thioethers [MeSB(12)H(11)](2-) (5), [1-(MeS)-2(7,12)-(Me(2)S)B(12)H(10)](-) (6-8), and [1,2(7,12)-(MeS)(2)B(12)H(10)](2-) (9-11) with alkyl halides and tosylates in acetonitrile. Since these methyl thioethers can be prepared easily in B-10-enriched form on a large scale and due to their chemical versatility, they are potentially very attractive boron entities for the design and synthesis of therapeutics for boron neutron capture therapy of cancer. It was found that alkylation of 6-8 can be complicated by an equilibrium which establishes between, on the one hand, one of the former species and, on the other hand, 1,2(7,12)-(Me(2)S)(2)B(12)H(10) (2-4) and [1,2(7,12)-(MeS)(2)B(12)H(10)](2-) (9-11). A boronated phosphonate 1-(MeS(CH(2))(4)P(O)(OEt)(2))-7-(Me(2)S)B(12)H(10) (14g) and a gem-bisphosphonate 1-(MeS(CH(2))(3)CH[P(O)(OEt)(2)](2))-7-(Me(2)S)B(12)H(10) (14h) were prepared from thioether 7 and the corresponding iodide and tosylate, respectively, and subsequently converted to their sodium salts. The propargyl sulfonium salts obtained by alkylation of thioethers 7, 8, 10, and 11 with propargyl bromide have been further converted to two- and three-cage oligomers containing both ortho-carborane and dodecaborane moieties. Methyl thioethers derived from closo-[B(12)H(12)](2-) are excellent participants in Michael addition reactions in the presence of a strong acid. The sulfonium salts with tertiary alkyl and vinyl substituents have been prepared by this method. Methyl thioethers 5-11 react with hydroxylamine-O-sulfonate yielding the corresponding aminosulfonium salts, albeit in lower yields as compared to those in the alkylation reactions. Several derivatives of methyl thioethers 5-11 have been characterized by single-crystal X-ray diffraction.

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Section: Methodsmentioning

confidence: 99%

Section: Synthesis Of Boronated Phosphonate and Gem-bisphosphonates B...mentioning

confidence: 99%

S-Alkylation and S-Amination of Methyl Thioethers − Derivatives ofcloso-[B₁₂H₁₂]^2-. Synthesis of a Boronated Phosphonate,gem-Bisphosphonates, and Dodecaborane-ortho-carborane Oligomers

Kultyshev

Liu

et al. 2002

J. Am. Chem. Soc.

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“…As far as azide‐containing BP precursors are concerned, only the synthesis of few examples of α‐azido and γ‐azido BPs have been described in the literature, but no click reactions have been reported for these compounds. Conversely, syntheses of and reactions with β‐azido BP are highly discussed topics .…”

Section: Resultsmentioning

confidence: 99%

Diketopyrrolopyrrole Bis‐Phosphonate Conjugate: A New Fluorescent Probe for In Vitro Bone Imaging

Chiminazzo

Borsato

Favero³

et al. 2019

Chemistry A European J

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The synthesis of a conjugate molecule between an unusual red‐fluorescent diketopyrrolopyrrole (DPP) unit and a bis‐phosphonate (BP) precursor by a click‐chemistry strategy to target bone tissue and monitor the interaction is reported. After thorough investigation, conjugation through a triazole unit between a γ‐azido rather than a β‐azido BP and an alkyne‐functionalized DPP fluorophore group turned out to be the winning strategy. Visualization of the DPP‐BP conjugate on osteoclasts and specific antiresorption activity were successfully demonstrated.

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“…Ethyl α ‐bromomethacrylate (EBBr), tert‐butyl α ‐bromometha‐crylate (TBBr), tetraethyl 4‐hydroxybutane‐1,1‐diyldiphosphonate and 3,3‐bis(diethoxyphosphoryl)propanoic acid were synthesized according to literature procedures . PEGMA (

{\overline{M}}_{normaln}

= 950), 2,2′‐azobis(isobutyronitrile) (AIBN), 2,2′‐dimethoxy‐2‐phenylacetophenone (DMPA), HAP, all other reagents and solvents were obtained from Aldrich Chemical Co. and used as received.…”

Section: Methodsmentioning

confidence: 99%

Synthesis and polymerizations of novel bisphosphonate-containing methacrylates derived from alkylα-hydroxymethacrylates

et al. 2013

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The synthesis and polymerizations of four novel bisphosphonate-containing monomers are reported. The monomers were synthesized from reaction of ethyl and tert-butyl α-bromomethacrylates with 3,3-bis(diethoxyphosphoryl)propanoic acid or with tetraethyl 4-hydroxybutane-1,1-diyldiphosphonate. Their thermal bulk polymerizations, photopolymerizations and copolymerizations with poly(ethylene glycol) methyl ether methacrylate were investigated. The homopolymerizations resulted in polymers with M n values of 25 000-83 000 g mol −1 ; the copolymerizations yielded soluble polymers with 22-34% incorporation of the new monomers; the photopolymerizations gave some structure-reactivity correlation; and one of the homopolymers, upon hydrolysis of its bisphosphonate groups, could interact with hydroxyapatite.

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A NEW EFFICIENT SYNTHESIS OF Ω-Aminoalkylidene-1,1-Bisphosphonate TETRAETHYLESTERS

Cited by 19 publications

References 12 publications

S-Alkylation and S-Amination of Methyl Thioethers − Derivatives ofcloso-[B₁₂H₁₂]^2-. Synthesis of a Boronated Phosphonate,gem-Bisphosphonates, and Dodecaborane-ortho-carborane Oligomers

S-Alkylation and S-Amination of Methyl Thioethers − Derivatives ofcloso-[B₁₂H₁₂]^2-. Synthesis of a Boronated Phosphonate,gem-Bisphosphonates, and Dodecaborane-ortho-carborane Oligomers

Diketopyrrolopyrrole Bis‐Phosphonate Conjugate: A New Fluorescent Probe for In Vitro Bone Imaging

Synthesis and polymerizations of novel bisphosphonate-containing methacrylates derived from alkylα-hydroxymethacrylates

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A NEW EFFICIENT SYNTHESIS OF Ω-Aminoalkylidene-1,1-Bisphosphonate TETRAETHYLESTERS

Cited by 19 publications

References 12 publications

S-Alkylation and S-Amination of Methyl Thioethers − Derivatives ofcloso-[B12H12]2-. Synthesis of a Boronated Phosphonate,gem-Bisphosphonates, and Dodecaborane-ortho-carborane Oligomers

S-Alkylation and S-Amination of Methyl Thioethers − Derivatives ofcloso-[B12H12]2-. Synthesis of a Boronated Phosphonate,gem-Bisphosphonates, and Dodecaborane-ortho-carborane Oligomers

Diketopyrrolopyrrole Bis‐Phosphonate Conjugate: A New Fluorescent Probe for In Vitro Bone Imaging

Synthesis and polymerizations of novel bisphosphonate-containing methacrylates derived from alkylα-hydroxymethacrylates

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S-Alkylation and S-Amination of Methyl Thioethers − Derivatives ofcloso-[B₁₂H₁₂]^2-. Synthesis of a Boronated Phosphonate,gem-Bisphosphonates, and Dodecaborane-ortho-carborane Oligomers

S-Alkylation and S-Amination of Methyl Thioethers − Derivatives ofcloso-[B₁₂H₁₂]^2-. Synthesis of a Boronated Phosphonate,gem-Bisphosphonates, and Dodecaborane-ortho-carborane Oligomers