A Route to 1‐Alkenylphosphine Derivatives via the Zr‐Catalyzed Reaction of 1‐Alkynylphosphines with Triethylaluminum

Ramazanov, Ilfir R.; Kadikova, Rita N.; Saitova, Zukhra R.; Джемилев, У. М.

doi:10.1002/ajoc.201500274

Cited by 13 publications

(14 citation statements)

References 35 publications

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“…strates that αor β-heteroatom-substituted alkynes react much more promptly than internal aliphatic alkynes, and thus enhances significantly the synthetic scope of the transformation by disclosing an efficient access to some heteroatom-functionalized alkenes with control of the double-bond geometry. The study represents an improvement over previous works on Zr-catalyzed cycloalumination of propargylamines 21 and alkynylphosphines 22 because the current catalytic system consisting of Et 2 Zn, Ti(O-iPr) 4 , and EtMgBr is more practical and less costly. Moreover, the dizincated species offer more potential for subsequent functionalization than the dialuminated species.…”

Section: Letter Syn Lettmentioning

confidence: 93%

“…Meanwhile, it is known that 1-alkynylphosphines, 1-alkynylphosphonates, propargylamines, 1-alkynyl selenides, and 1-alkynyl sulfides are efficient substrates for the preparation of zirconacyclopentenes [17][18][19][20] and aluminacyclopentenes. [21][22][23][24] Regarding 2-zincoethylzincation, only one case of the preparation of organozinc derivative in 63% yield only after 4 days using the Ti-Mg-catalyzed reaction of 5decyne with Et 2 Zn has been reported in the literature. 25 However, this reaction is a unique example of carbozincation of the triple carbon-carbon bond with Et 2 Zn using oxidative coupling of ethylene and 5-decyne on titanium(II) in catalytic cycle.…”

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confidence: 99%

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2-Zincoethylzincation of 2-Alkynylamines and 1-Alkynylphosphines Catalyzed by Titanium(IV) Isopropoxide and Ethylmagnesium Bromide

Kadikova

Ramazanov²,

Mozgovoi³

et al. 2019

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Titanium(IV) isopropoxide and ethylmagnesium bromide catalyzed reaction of 2-alkynylamines with Et2Zn, followed by deuterolysis/hydrolysis and iodinolysis, affords substituted (Z)-pent-2-en-2,5-d 2-1-amines, (Z)-pent-2-en-1-amines (65–88%), and substituted (Z)-2,5-diiodopent-2-en-1-amines (55–63%). It is suggested that the reaction proceeds through the formation of cyclic organotitanium derivatives. The reaction between 1-alkynylphosphines and Et2Zn in the presence of catalytic amounts of Ti(O-iPr)4 and EtMgBr leads to trisubstituted 1-alkenylphosphine oxides with high regioselectivity and stereoselectivity.

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Section: Letter Syn Lettmentioning

confidence: 93%

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confidence: 99%

2-Zincoethylzincation of 2-Alkynylamines and 1-Alkynylphosphines Catalyzed by Titanium(IV) Isopropoxide and Ethylmagnesium Bromide

Kadikova

Ramazanov²,

Mozgovoi³

et al. 2019

Synlett

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“…46 Generally, it is consistent with our earlier views about the key role of zirconocene-ethylene intermediate in this reaction. 47 While considering the Zr-catalyzed reaction of Et 3 Al with propargyl alcohols, propargylamines, 37 and 1-alkynylphosphines, 38 we suggested that the Et 2 AlCl molecule located in the zirconacyclopropene coordination sphere is the principal factor determining the regioselectivity of cycloalumination. Similarly, in the case of cycloalumination of 1-alkynyl selenides, one can assume the formation of stable five-membered cyclic complex (Scheme 2).…”

Section: Scheme 1 Zr-catalyzed сYcloalumination Of 1-alkynyl Selenidementioning

confidence: 98%

“…35,36 As an alternative, recently we developed regio-and stereoselective methods for the preparation of О-, N-, and P-containing alkenes by Cp 2 ZrCl 2catalyzed cycloalumination of propargyl and homopropargyl alcohols, propargylamines, 37 and 1-alkynylphosphines. 38 The efficiency of carboalumination for the synthesis of P-and S-containing alkenes was demonstrated by Cp 2 ZrCl 2 -catalyzed ethylalumination of 1-alkynyl phosphorus oxides 39 and methylalumination of alkynyl sulfones, sulfoxides, and sulfides. 40 Thus, carboalumination of alkynes is an efficient method for the synthesis of various functionally substituted alkenes.…”

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confidence: 99%

Zirconium-Catalyzed Alkyne Carbo- and Cycloalumination Reactions in Stereoselective Preparation of 1-Alkenyl Selenides

et al. 2017

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Supporting informationThe reagents were obtained from Sigma-Aldrich or Acros. Dichloromethane and hexane were distilled over P 2 O 5 . Organic diselenides were prepared by the reaction of elemental selenium with hydrazine hydrate and bromobenzene or bromoalkane under the action of sodium hydroxide solution in DMF [1]. The alkynyl selenides were prepared by the reaction of terminal alkynes with elemental selenium and bromoalkanes [2]. IR spectra were recorded on Bruker VE Vertex 70v spectrometer as liquid films or in Nujol and are reported in wavenumbers (cm -1 ).Nuclear magnetic resonance spectroscopy was performed on a Brucker Avance 400. The 1 H NMR spectra were recorded at 400 MHz and 13 C NMR spectra at 100 MHz in CDCl 3 . The chemical shifts are reported in ppm relative to tetramethylsilane (TMS) as the internal standard. The numbering of atoms in the 13 С and 1 H NMR spectra of the compounds A-F and 2a-f, 3b-e, 4a-e, 5b, 7a-f, 8ac is shown in Figures 1,2,3,4,5. Elemental analysis was performed using a Carlo-Erba CHN 1106 elemental analyser. Mass spectra were obtained on a Finnigan 4021 instrument. The yields were calculated from the isolated amount of 1-alkenyl selenides obtained from starting alkynes. All quantum-chemical calculations were performed using B3LYP/6-31G(d,p) basis set as implemented in Gaussian 09 software [3]. Preparation of alkynyl selenides A-F by the reaction of alkynyl lithium with elemental Se and bromoalkanes Figure 1The numbering of atoms in the 13 Сand 1 H-NMR spectra of the compounds A-F Butyl(hex-1-yn-1-yl)selenide (A)To a two-neck round-bottomed flask, under argon, containing a solution of hex-1yne (820 mg, 10 mmol) in THF (30 mL) at -78 o C was added to n-BuLi (4.0 mL of a 2.5M solution in hexane; 10 mmol). The reaction mixture was stirred for 30 min.After this the reaction was warmed to 0 o C and elemental selenium (800 mg; 10 mmol) was added. The reaction was allowed to stir at reflux for 5 h. After this time, the reaction was cooled to room temperature and then the butyl bromide (685 mg, 5 mmol) was added. The reaction mixture was allowed to stir at room temperature for additional 12 h. After this time, the mixture was diluted with ethyl acetate (20 mL) and washed with saturated aqueous NH 4 Cl (20 mL) and water (3×20 mL). The organic phase was separated, dried over MgSO 4 . Evaporation of solvent and purification of the residue by column chromatography (silica gel, petroleum ether) gave a colourless oil; yield: 1800 mg (83%); R f = 0.72 (petroleum ether). Butyl(hept-1-yn-1-yl)selenide (B)Using the procedure described above hept-1-yne (960 mg, 10 mmol) and 1bromobutane (685 mg, 5 mmol) gave a crude product that was purified by flash chromatography (silica gel, petroleum ether) to afford a colorless oil; yield: 1825 mg (79%); Rf = 0.77 (petroleum ether).Butyl(oct-1-yn-1-yl)selenide (C)Using the procedure described above hept-1-yne (960 mg, 10 mmol) and 1bromobutane (685 mg, 5 mmol) gave a crude product that was purified by flash chromatography (silica gel, petroleum ether) to a...

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“…1 Previously, we developed methods for the preparation of 1-alkenyl phosphines and phosphine oxides based on Zr-catalyzed carboalumination of 1-alkynyl phosphines and phosphine oxides. 2,3 It has been found that the pathway of the reaction of 1-alkynyl phosphine derivatives with organoaluminum compounds strongly depends on the nature of the substrate and the solvent. The ethylalumination takes place under the action of Et 3 Al in the case of 1-alkynyl phosphines and phosphine oxides in hexane as the solvent.…”

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Zirconocene Catalysis in Organoaluminum Synthesis of 1-Alkenyl Sulfones and Sulfides

et al. 2016

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A Route to 1‐Alkenylphosphine Derivatives via the Zr‐Catalyzed Reaction of 1‐Alkynylphosphines with Triethylaluminum

Cited by 13 publications

References 35 publications

2-Zincoethylzincation of 2-Alkynylamines and 1-Alkynylphosphines Catalyzed by Titanium(IV) Isopropoxide and Ethylmagnesium Bromide

2-Zincoethylzincation of 2-Alkynylamines and 1-Alkynylphosphines Catalyzed by Titanium(IV) Isopropoxide and Ethylmagnesium Bromide

Zirconium-Catalyzed Alkyne Carbo- and Cycloalumination Reactions in Stereoselective Preparation of 1-Alkenyl Selenides

Zirconocene Catalysis in Organoaluminum Synthesis of 1-Alkenyl Sulfones and Sulfides

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