Organophosphorus compounds. XVI. 2-(N-Dialkylamino)alkyldiphenylphosphines, phosphine oxides and sulphides as analogues of methadone

A series of 2-(N-dialkylamino)ethyldiphenylphosphine oxides and sulphides was prepared by the addition of a secondary amine to diphenylvinylphosphine oxide, or the phosphine sulphide, respectively. Similarly, a series of 2-(N-dialkylamino)propyldiphenylphosphine oxides was prepared from diphenylprop-1-enylphosphine oxide, or from diphenylprop-2-enylphosphine oxide which isomerized under the reaction conditions. Reduction of the 2-(N-dialkylamino)propyldiphenylphosphine oxides with trichlorosilane, and oxidation of the phosphines with sulphur, afforded the corresponding phosphine sulphides. �� None of the compounds showed significant analgesic activity.

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Primary Phosphines and Phosphine Oxides with a Stereogenic Carbon Center Adjacent to the Phosphorus Atom: Synthesis and Anti-Markovnikov Radical Addition to Alkenes

Organics ◽

10.3390/org2040023 ◽

2021 ◽

Vol 2 (4) ◽

pp. 395-403

Author(s):

Toshiaki Murai ◽

Ryota Wada ◽

Kouji Iwata ◽

Yuuki Maekawa ◽

Kazuma Kuwabara ◽

...

Keyword(s):

Carbon Atom ◽

Phosphorus Atom ◽

Organophosphorus Compounds ◽

Radical Addition ◽

Secondary Phosphine ◽

Phosphine Oxides ◽

Reaction Conditions ◽

High Yields ◽

Oxidized Products

Organophosphorus compounds with stereogenic phosphorus and carbon atoms have received increasing attention. In this regards, primary phosphines with a stereogenic carbon atom adjacent to the phosphorus atom were synthesized by the reduction in phosphonates and phosphonoselenoates with a binaphthyl group. Their oxidized products, i.e., phosphine oxides with a stereogenic tetrasubstituted carbon atom, were found to undergo BEt3-mediated radical addition to cyclohexene to give P-stereogenic secondary phosphine oxides with a diastereoselectivity of 91:9. The products were characterized by ordinary analytical methods, such as Fourier transform infrared spectroscopy; 1H, 13C, and 31P NMR spectroscopies; and mass spectroscopy. Computational studies on the phosphorus-centered radical species and the obtained product implied that the thermodynamically stable radical and the adduct may be formed as a major diastereomer. The radical addition to a range of alkenes took place in an anti-Markovnikov fashion to give P-stereogenic secondary phosphine oxides. A variety of functional groups in the alkenes were tolerated under the reaction conditions to afford secondary phosphine oxides in moderate yields. Primary phosphines with an alkenyl group, which were generated in situ, underwent intramolecular cyclization to give five- and six-membered cyclic phosphines in high yields after protection by BH3.

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Organophosphorus compounds. XI. Synthesis of some 1,2,3,4,5,6-Hexahydro-1,5-methano-4,1-benzazaphosphocines

Australian Journal of Chemistry ◽

10.1071/ch9740815c ◽

1974 ◽

Vol 27 (4) ◽

pp. 815 ◽

Cited By ~ 7

Author(s):

DJ Collins ◽

LE Rowley ◽

JM Swan

Keyword(s):

Analgesic Activity ◽

Acid Chloride ◽

Organophosphorus Compounds ◽

Mild Conditions ◽

Tricyclic Compounds ◽

Vinyl Group ◽

Successive Reduction

1-Hydroxy-1,2,3,4-tetrahydrophosphinoline 1-oxide (2a) was converted via the corresponding acid chloride (2b) into the 1-vinylphosphine oxide (3) which underwent a Michael-like addition with dimethylamine to give 1-(2'-dimethylaminoethyl)-1,2,3,4-tetrahydrophosphinoline 1-oxide (6). The successive reduction of (6) with trichlorosilane, and oxidation with sulphur afforded the phosphine sulphide (7). The reaction of 1-vinyl-1,2,3,4-tetrahydrophosphinoline 1-oxide (3) with N-bromosuccinimide followed by treatment with dimethylformamide gave 1-vinyl-1,2-dihydrophosphinoline 1-oxide which, under mild conditions, underwent Michael-like addition of amines to the vinyl group to give, for example, 1-(2'-propylaminoethy1)-1,2-dihydrophosphinoline 1-oxide. When heated in a sealed tube at 140-150° in water for 60 h this amine was converted into 4-propyl-1,2,3,4,5,6-hexa- hydro-1,5-methano-4,1-benzazaphosphocine 1-oxide. Several related tricyclic compounds including the corresponding phosphines and phosphine sulphides were synthesized. Several of the new aminophosphorus compounds were tested for analgesic activity.

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Nickel-catalyzed annulations of ortho-haloarylimines

10.21203/rs.3.rs-526421/v1 ◽

2021 ◽

Author(s):

Srinivas Kolluru ◽

Manvendra Singh ◽

Bryce Gaskins ◽

Zarko Boskovic

Keyword(s):

Activation Energy ◽

Secondary Amine ◽

Oxidative Addition ◽

Reaction Conditions ◽

Quantitative Manner

Abstract We report the discovery, development, and mechanism of a nickel-catalyzed annulation reaction between o-haloarylimines and electron-poor olefins. The reaction produces two adjacent anti stereocenters and a free secondary amine. Spirocycles are formed from cyclic imines. We characterized the key oxidative addition intermediate and identified a major path leading to competing homo-coupling products. The activation energy of oxidative addition, and the rate of oxidative addition complex isomerization were determined. Sensitivity of the reaction to reaction conditions was established in a quantitative manner and both the scope and limitations of the method are presented.

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Catalyst- and Solvent-Free Addition of the P–H Species to Alkenes and Alkynes: A Green Methodology for C–P Bond Formation

Synthesis ◽

10.1055/s-0036-1588542 ◽

2017 ◽

Vol 49 (21) ◽

pp. 4783-4807 ◽

Cited By ~ 14

Author(s):

Boris Trofimov ◽

Nina Gusarova ◽

Nataliya Chernysheva

Keyword(s):

Organophosphorus Compounds ◽

Bond Formation ◽

Solvent Free ◽

Secondary Phosphine ◽

Phosphine Oxides ◽

Secondary Phosphine Chalcogenides ◽

Vinyl Sulfides ◽

Radical Initiators ◽

Phosphine Chalcogenides ◽

Secondary Phosphines

Traditional methods for C–P bond formation via direct addition of P–H species to unsaturated compounds are usually implemented in the presence of base and metal catalysts or radical initiators in various organic solvents. During the last five years, a novel efficient and general catalyst/initiator- and solvent-free version of the hydrophosphination and hydrophosphinylation of multiple C–C bonds with H-phosphines and their chalcogenides has begun to develop and it is attracting growing attention. This approach corresponds to the recently emerged pot-, atom-, and step-economy (PASE) green paradigm. This review covers the literature on the synthesis of useful and in-demand organophosphorus compounds via catalyst- and solvent-free addition of P–H species to alkenes and alkynes.1 Introduction2 Addition of Secondary Phosphines to Alkenes3 Hydrophosphinylation of Alkenes with Secondary Phosphine Chalcogenides3.1 Oxidative Addition of Phosphine Oxides to Vinyl Sulfides3.2 Addition of Secondary Phosphine Sulfides and Phosphine Selenides to Alkenes3.3 Addition of Secondary Phosphine Sulfides and Phosphine Selenides to Divinyl Chalcogenides3.4 Hydrophosphinylation of Alkenes with Secondary Phosphine/Chalcogen Pair (Three-Component Reactions)4 Addition of Secondary Phosphines to Alkynes5 Addition of Secondary Phosphine Chalcogenides to Alkynes6 Conclusion

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Organophosphorverbindungen mit tertiären Alkylsubstituenten. III*: Synthese und Reaktionen Di-1-adamantylsubstituierter Phosphorverbindungen; Kristallstruktur von Di-1-Adamantylphosphinsäurechlorid / Organophosphorus Compounds with Tertiary Alkyl Substituents. Ill: Synthesis and Reactions of Di-1-adam antyl-Substituted Phosphorus Compounds; Crystal Structure of Di-1-adam antylphosphinic Chloride

Zeitschrift für Naturforschung B ◽

10.1515/znb-1994-0614 ◽

1994 ◽

Vol 49 (6) ◽

pp. 801-811 ◽

Cited By ~ 19

Author(s):

Jens R. Goerlich ◽

Axel Fischer ◽

Peter G. Jones ◽

Reinhard Schmutzler

Keyword(s):

Organophosphorus Compounds ◽

Phosphorus Compounds ◽

Secondary Phosphine ◽

Phosphine Oxides ◽

X Ray ◽

Dry Air ◽

Nmr Data ◽

Standard Procedures ◽

Hydrolysis Of ◽

Tertiary Alkyl

The reaction of adamantane with PCl3/A1Cl3, followed by hydrolysis, gave (1-Ad)2P(:O)Cl 1, which was converted to (1-Ad)2P(:O)F 2 and (1-Ad)2P(:S)Cl 3 by standard procedures. The structure of 1 was confirmed by a single crystal X-ray structure determination; despite the bulky substituents the P-C bond lengths are normal (184.0(3), 185.0(3) pm). Whereas chlorine-fluorine exchange in 3 with AsF3 furnished (1-Ad)2P(:S)F 4, desulfuration of 3 with Ph3P to give (1-Ad)2PCl 5 failed. The secondary phosphine oxides R 1R2P(:O)H (R1, R2 = 1-Ad: 6; R1 = 1-Ad, R2 = tBu: 7; R1, R2 = tBu: 8) were synthesized by reaction of 1, 1-AdP(:O)Cl2 and tBuP(:0)Cl2 with tBuLi. 6 and 8 reacted readily with chloral to give the adducts R2P(:O)CH(OH)CCl3 (R = 1-Ad: 9; R = tBu: 10). Silylation of 6 with Me2NSiMe3 in the presence of dry air led to (1-Ad)2P(:O)OSiMe3 11, which was hydrolyzed to give (1-Ad)2P(:O)OH 12. (1-Ad)2POSiMe3 13 was obtained by the reaction of 6 with n-BuLi, followed by Me3SiCl. No reaction took place upon heating 6 with Mo(CO)6. (1-Ad)2PCl 5 was synthesized in low yield by the reaction of 6 with PCl3. The action of tetrachloro-obenzoquinone (TOB) upon 6 furnished (1-Ad)2P(:O)(o-OH)C6Cl4 15, whereas the tbutyl analogue of 15, 16, was synthesized by hydrolysis of the TOB-adduct of di-tbutylfluorophosphine. Analogous 1-adamantyl- and tbutyl-phosphorus compounds are compared with regard to their 31P NMR data

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Chloroform-based Atherton–Todd-type reactions of alcohols and thiols with secondary phosphine oxides generating phosphinothioates and phosphinates

RSC Advances ◽

10.1039/c5ra16015d ◽

2015 ◽

Vol 5 (88) ◽

pp. 71544-71546 ◽

Cited By ~ 29

Author(s):

Shan Li ◽

Tieqiao Chen ◽

Yuta Saga ◽

Li-Biao Han

Keyword(s):

Functional Groups ◽

Secondary Phosphine ◽

Phosphine Oxides ◽

Reaction Conditions

Various valuable phosphinothioates and phosphinates including those with functional groups are readily prepared under mild reaction conditions via chloroform-based Atherton–Todd-type reactions of secondary phosphine oxides with alcohols and thiols, respectively.

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Palladium-Catalyzed C–P Cross-Coupling between (Het)aryl Halides and Secondary Phosphine Oxides

Synthesis ◽

10.1055/s-0037-1610698 ◽

2019 ◽

Vol 51 (11) ◽

pp. 2379-2386 ◽

Cited By ~ 3

Author(s):

Gladis Zakirova ◽

Dmitrii Mladentsev ◽

Nataliya Borisova

Keyword(s):

Electronic Properties ◽

Heterocyclic Compounds ◽

Cross Coupling ◽

Secondary Phosphine ◽

Phosphine Oxides ◽

Tertiary Phosphine ◽

Reaction Conditions ◽

Efficient Procedure ◽

Palladium Catalyzed ◽

Tertiary Alkyl

An efficient procedure for C–P bond formation via the palladium-catalyzed [Pd(OAc)2/dppf/Cs2CO3] reaction between dichloroheterocycles and secondary phosphine oxides was developed. The steric and electronic properties of substituents were varied to establish the scope and limitations of the method developed. By applying these conditions, a variety of new heterocyclic compounds bearing two tertiary phosphine oxides were successfully synthesized in moderate to excellent yields. After adjustments to the reaction conditions [Pd(OAc)2/dippf/t-BuOK], cross-coupling of secondary phosphine oxides with bulky (secondary or tertiary alkyl) substituents on the phosphorus atom was achieved. Extension of the methodology to monohalohetarenes and monohaloarenes was successfully carried out; once again, the steric and electronic properties of the halides were varied widely. The desired reaction occurred in all cases studied, giving high to excellent yields of product regardless of the nature and positions of substituents.

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