Chemo- and Regiospecific Monoaddition of Secondary Phosphine Sulfides to 1-Acyl-2-phenylacetylenes

Glotova, T. E.; Dvorko, Marina Yu.; Гусарова, Н. К.; Arbuzova, S. N.; Ushakov, Igor А.; Kazantseva, T. I.; Трофимов, Б. А.

doi:10.1080/10426500701648069

Cited by 14 publications

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References 23 publications

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“…This reaction is at the time under intensive study on the example of "activated" acetylenes with the triple bond bearing electron with drawing groups. 13- 16 The reaction of acetylene and its first and the most available homolog (methylacetylene) with secondary phosphine sulfides has not been imple mented so far. Moreover, it was reported 13 that diphenyl phosphine sulfide does not react with electron saturated acetylenes (hexyne, phenylacetylene) under nucleophilic conditions, for example, in the system КОH-…”

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Nucleophilic diaddition of secondary phosphine sulfides to acetylene and methylacetylene

et al. 2009

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Secondary phosphine sulfides react with acetylene and methylacetylene in the system КOH-DMSO (50 °C, 2-3 h) to form the corresponding tertiary bis phosphine sulfides in high yield (up to 97%). Specific features of the NMR spectra ( 1 H, 13 C, and 31 P) of compounds obtained are discussed.Bis phosphine sulfides are under intensive study as efficient polydentate ligands for the design of metal com plex catalysts, 1-4 antipyrenes, 5 intermediate products for the development of fluorescent and electroluminescent sensors, 6 as well as promising solvents and intermediates for the preparation of semiconducting nanomaterials. 7 Bis phosphine sulfides with chiral centers are of particular value. 8 Reduction of the latter leads to the corresponding optically active bis phosphines, 9 which are widely used in the catalytic stereoselective synthesis. 10,11 At the same time, methods for the preparation of bis phosphine sul fides, as a rule, are multistep and laborious and are based on toxic phosphorus halides and organometallic reagents. 12 One of the most convenient approaches to the synthesis of tertiary bis phosphine chalcogenides is the reaction of nucleophilic addition of two molecules of secondary phos phine chalcogenide to acetylenes. This reaction is at the time under intensive study on the example of "activated" acetylenes with the triple bond bearing electron with drawing groups. 13-16 The reaction of acetylene and its first and the most available homolog (methylacetylene) with secondary phosphine sulfides has not been imple mented so far. Moreover, it was reported 13 that diphenyl phosphine sulfide does not react with electron saturated acetylenes (hexyne, phenylacetylene) under nucleophilic conditions, for example, in the system КОH-H 2 OMeCN.In the present work, in order to develop a straight forward method for the synthesis of new bis phosphine sulfides, the reaction of nucleophilic addition of second ary phosphine sulfides 1a,b, easily available from styrenes, * Dedicated to Academician A. I. Konovalov in honor of his 75th anniversary. red phosphorus, and elementary sulfur, to acetylene and methylacetylene has been studied. 17,18 Experiments showed that virtually no reaction takes place in the system КОH-THF. At the same time, when superbasic catalytic system КОH-DMSO 19 was used, the nucleophilic addition of two molecules of secondary phos phine sulfide proceeds efficiently at mild temperatures (50 °C, 2-3 h) under pressure of acetylene (autoclave, the initial pressure of 14 atm) or in the channel system (in the case of methylacetylene) with the formation of bis adducts 2a-c in high yield (Scheme 1). Scheme 1R 1 = R 2 = H (a); R 1 = Bu t , R 2 = H (b); R 1 = H, R 2 = Me (c)

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Nucleophilic diaddition of secondary phosphine sulfides to acetylene and methylacetylene

et al. 2009

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“…It is known that secondary phosphine halides react with electron-deficient acetylenes in the presence of bases [1][2][3][4], radical initiators [1,5,6], metal complex catalysts [7,8], under microwave irradiation [9], and (rarely) in bulk without any catalyst [10] to form tertiary alkenylphosphine halides and the products of bis-addition.…”

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“…Zwitterion A was in equilibrium with the zwitterion C (carbanionic center is cis position DOI: 10.1134/S1070363215080319 R 1 = Ph (Ia, IVa, Va), R 2 = H, R 3 = Me (IIa, IVa, Va), R 4 = Me (IIIa, IVa), X = S (Ia, IVa, Va); R 1 = PhCH 2 CH 2 (Ib, IVb, Vb), R 2 = EtO 2 C, R 3 relative to the nitrogen atom). The allene intermediate B was involved in that equilibrium as well.…”

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Synthesis of new N-phosphorylated vinylhydropyridines

et al. 2015

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It is known that secondary phosphine halides react with electron-deficient acetylenes in the presence of bases [1][2][3][4], radical initiators [1,5, 6], metal complex catalysts [7,8], under microwave irradiation [9], and (rarely) in bulk without any catalyst [10] to form tertiary alkenylphosphine halides and the products of bis-addition.In this work, we performed a three-component reaction of diphenylphosphine sulfide Ia and bis(2-phenylethyl)phosphine selenide Ib with acetylenecarboxylates IIa, IIb and pyridines IIIa, IIIb. The reaction occurred under mild conditions (20-52°C, 1-5 h, MeCN) and led to the regio-and stereoselective formation of (E)-N-ethenyl-1,4-dihydropyridines IVa and IVb with yield of 47 and 17%, respectively. In addition, compounds Va and Vb were obtained (up to 63%) as a result of nucleophilic addition of PHcompounds at the triple bond of alkynes II (Scheme 1).Furthermore, formation of the bis-adduct Ph 2 P(=S) CH 2 CH(CO 2 Me)(S=P)Ph 2 IVa was detected in the reaction of phosphine Ia with propiolate IIa in the presence of 2-methylpyridine IIIa.Probably, the reaction pathway included nucleophilic addition of pyridine at the triple bond of electrophilic acetylene, leading to zwitter ion A with carbanionic site trans-positioned with respect to the nitrogen atom. Zwitterion A was in equilibrium with the zwitterion C (carbanionic center is cis position R 1 = Ph (Ia, IVa, Va), R 2 = H, R 3 = Me (IIa, IVa, Va), R 4 = Me (IIIa, IVa), X = S (Ia, IVa, Va); R 1 = PhCH 2 CH 2 (Ib, IVb, Vb), R 2 = EtO 2 C, R 3 = Et (IIb, IVb, Vb), R 4 = H (IIIb, IVb), X = Se (Ib, IVb, Vb). O OR 3 N R 4 R 2 + 20 _ 52 о C, 1 _ 5 h MeCN Ia, Ib IIa, IIb + R 1 2 P X H N R 1 2 P X R 4 H IIIa, IIIb R 2 H R 1 2 P X C + Scheme 1.

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“…11,12 Moreover, under basic conditions [KOH in dimethyl sulfoxide (DMSO) or KOH in tetrahydrofuran (THF)], the secondary phosphine sulfides add to alkynes (acetylene and methyl-acetylene, 13 phenylcyanoacetylene 14 ) to give 1,2-diadducts in good yields. In case of 4-hydroxy-4-methyl-2-pentynenitrile 15 and 1-acyl-2-phenylacetylenes, 16 this reaction stops at the stage of monoadduct formation.…”

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Catalyst- and Solvent-Free Stereoselective Addition of Secondary Phosphine Chalcogenides to Alkynes

et al. 2014

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Chemo- and Regiospecific Monoaddition of Secondary Phosphine Sulfides to 1-Acyl-2-phenylacetylenes

Cited by 14 publications

References 23 publications

Nucleophilic diaddition of secondary phosphine sulfides to acetylene and methylacetylene

Nucleophilic diaddition of secondary phosphine sulfides to acetylene and methylacetylene

Synthesis of new N-phosphorylated vinylhydropyridines

Catalyst- and Solvent-Free Stereoselective Addition of Secondary Phosphine Chalcogenides to Alkynes

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