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

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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Air and water stable secondary phosphine oxides as diazaphospholene precatalysts

Chemical Communications ◽

10.1039/d0cc01072c ◽

2020 ◽

Vol 56 (58) ◽

pp. 8027-8030 ◽

Cited By ~ 4

Author(s):

Travis Lundrigan ◽

Chieh-Hung Tien ◽

Katherine N. Robertson ◽

Alexander W. H. Speed

Keyword(s):

Secondary Phosphine ◽

Phosphine Oxides

Secondary phosphine oxides, which are air and water stable, and purifiable by chromatography generate phosphenium or phosphorus hydride catalysts in situ.

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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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Palladium-catalyzed dehydrogenative coupling of terminal alkynes with secondary phosphine oxides

Chemical Communications ◽

10.1039/c4cc09567g ◽

2015 ◽

Vol 51 (17) ◽

pp. 3549-3551 ◽

Cited By ~ 32

Author(s):

Jia Yang ◽

Tieqiao Chen ◽

Yongbo Zhou ◽

Shuangfeng Yin ◽

Li-Biao Han

Keyword(s):

Reaction Mechanism ◽

Palladium Acetate ◽

Secondary Phosphine ◽

Terminal Alkynes ◽

Phosphine Oxides ◽

Dehydrogenative Coupling ◽

Palladium Catalyzed ◽

High Yields

The palladium-catalyzed dehydrogenative coupling of alkynes with secondary phosphine oxides is developed. Thus, in the presence of a silver additive, palladium acetate could efficiently catalyze the dehydrocoupling of secondary phosphine oxides with a variety of alkynes to produce the corresponding alkynylphosphine oxides in high yields. A reaction mechanism is proposed.

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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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One-Step Synthesis of Acylboron Compounds via Cu-Catalyzed Carbonylative Borylation of Alkyl Halides

10.26434/chemrxiv.12818180 ◽

2020 ◽

Author(s):

Cheng Li-Jie ◽

Zhao Siling ◽

Neal Mankad

Keyword(s):

Alkyl Halides ◽

Efficient Synthesis ◽

Mechanistic Studies ◽

Acyl Halide ◽

Reaction Conditions ◽

One Pot ◽

One Step ◽

High Yields ◽

Tertiary Alkyl

A Cu-catalyzed carbonylative borylation of unactivated alkyl halides has been developed, enabling efficient synthesis of aliphatic potassium acyltrifluoroborates (KATs) in high yields by treating the in-situ formed tetracoordinated acylboron intermediates with aqueous KHF2. A variety of functional groups are tolerated under the mild reaction conditions, and primary, secondary and tertiary alkyl halides are all applicable. In addition, this method also provides facile access to N-methyliminodiacetyl (MIDA) acylboronates as well as α-methylated potassium acyltrifluoroborates in a one-pot manner. Mechanistic studies indicate a radical atom transfer carbonylation (ATC) mechanism to form acyl halide intermediates that are subsequently borylated by (NHC)CuBpin.<br>

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

Australian Journal of Chemistry ◽

10.1071/ch9742365 ◽

1974 ◽

Vol 27 (11) ◽

pp. 2365 ◽

Cited By ~ 21

Author(s):

DJ Collins ◽

S Mollard ◽

N Rose ◽

JM Swan

Keyword(s):

Analgesic Activity ◽

Secondary Amine ◽

Organophosphorus Compounds ◽

Phosphine Oxides ◽

Reaction Conditions ◽

Diphenylvinylphosphine Oxide

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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Multicomponent versus domino reactions: One-pot free-radical synthesis of β-amino-ethers and β-amino-alcohols

Beilstein Journal of Organic Chemistry ◽

10.3762/bjoc.11.10 ◽

2015 ◽

Vol 11 ◽

pp. 66-73 ◽

Cited By ~ 7

Author(s):

Bianca Rossi ◽

Nadia Pastori ◽

Simona Prosperini ◽

Carlo Punta

Keyword(s):

Free Radical ◽

Cyclic Ether ◽

Radical Addition ◽

Domino Reaction ◽

Alcohol Molecule ◽

Secondary Products ◽

Reaction Conditions ◽

One Pot ◽

Mild Conditions

Following an optimized multicomponent procedure, an aryl amine, a ketone, and a cyclic ether or an alcohol molecule are assembled in a one-pot synthesis by nucleophilic radical addition of ketyl radicals to ketimines generated in situ. The reaction occurs under mild conditions by mediation of the TiCl4/Zn/t-BuOOH system, leading to the formation of quaternary β-amino-ethers and -alcohols. The new reaction conditions guarantee good selectivity by preventing the formation of secondary products. The secondary products are possibly derived from a competitive domino reaction, which involves further oxidation of the ketyl radicals.

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Gold(I)-catalyzed intramolecular cyclization/intermolecular cycloaddition cascade as a fast track to polycarbocycles and mechanistic insights

Nature Communications ◽

10.1038/s41467-021-21335-9 ◽

2021 ◽

Vol 12 (1) ◽

Author(s):

Cheng Zhang ◽

Kemiao Hong ◽

Chao Pei ◽

Su Zhou ◽

Wenhao Hu ◽

...

Keyword(s):

Fast Track ◽

Cycloaddition Reaction ◽

Structural Diversity ◽

Mechanistic Studies ◽

Reaction Conditions ◽

In Situ Formation ◽

Increasing Demand ◽

High Yields ◽

Synthetic Intermediate

AbstractMetal carbene is an active synthetic intermediate, which has shown versatile applications in synthetic chemistry. Although a variety of catalytic methods have been disclosed for the generation of carbene species from different precursors, there is an increasing demand for the development of efficient and practical approaches for the in-situ formation of metal carbene intermediates with structural diversity and unrevealed reactivity. Herein we report a gold-catalyzed cascade protocol for the assembly of polycarbocyclic frameworks in high yields under mild reaction conditions. Mechanistic studies indicate that the unique β-aryl gold-carbene species, generated via gold-promoted 6-endo-dig diazo-yne cyclization, is the key intermediate in this reaction, followed by a [4 + 2]-cycloaddition with external alkenes. In comparison to the well-documented metal carbene cycloadditions, this carbene intermediate serves as a 4-C synthon in a cycloaddition reaction. A variety of elusive π-conjugated polycyclic hydrocarbons (CPHs) with multiple substituents are readily accessible from the initially generated products by a mild oxidation procedure.

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