Palladium(II) aminoiminophosphoranate complexes as cross-coupling catalysts

Peganova, T. A.; Kalsin, Alexander M.; Ustynyuk, Nikolai A.; Васильев, А. А.

doi:10.1007/s11172-014-0739-8

Cited by 9 publications

(3 citation statements)

References 49 publications

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“…The main product obtained was the monoallyl derivative, whereas coupling gave rise to the diallyl derivative when a conventional phosphine or diamidophosphite based Pd(0) catalyst was present. 8 In 2018, a stereoselective intramolecular Tsuji-Trost cascade cyclization of (homo)allylic vicinal diacetates with a pendant -ketoamide 19 or related carbon nucleophile was reported to give -lactam-fused vinylcyclopropanes 20. In addition to two new rings, the products contain three contiguous new carbon stereocenters, two of them are qua-ternary, with a 9:1 dr. 9 Moreover, the reaction proceeded with >94% enantiospecificity with optically enriched starting materials, using an inexpensive carbohydrate as the source of chirality (Scheme 6).…”

Section: N-allylationmentioning

confidence: 99%

π-Allylpalladium Complexes in Synthesis: An Update

Parisotto¹,

Deagostino²

2019

Synthesis

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This review aims to summarize the development of the chemistry of π-allylpalladium complexes both as intermediates and catalysts/reagents between 2013 and early 2109. Major attention has been devoted to the synthetic aspect of these versatile intermediates.1 Introduction2 π-Allylpalladium Complexes Generated from Allyl Electrophiles2.1 Activated Allylic Compounds2.2 Unactivated Allylic Compounds: Allylic Alcohols and Hydrocarbons2.3 Total Syntheses3 π-Allylpalladium Complexes Generated from Dienes3.1 Conjugated Dienes3.2 Allenes4 π-Allylpalladium Complexes Exploited as Reactants and Precatalysts4.1 Allylpalladium-Catalyzed Dehydrogenation4.2 Allylpalladium-Catalyzed Synthesis of Alkenylboronic Esters4.3 Allylpalladium-Based Precatalysts5 Conclusions

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Section: N-allylationmentioning

confidence: 99%

π-Allylpalladium Complexes in Synthesis: An Update

Parisotto¹,

Deagostino²

2019

Synthesis

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“…The interest in iminophosphonamines Ph 2 P(NR)(NHR′) has been constantly growing due to their potential use as superbases in asymmetric Brønsted base organocatalysis 1 and as  2 -N,N chelate ligands for the synthesis of transition metal iminophosphonamides. The latter have been reported as active catalysts for alkene polymerization, 2 3,4-selective polymerization of isoprene, 3 alkene oligomerization, 4 ethene dimerization, 2c cyclopropanation, 5 and aziridination, 6 as well as for Tsuji-Trost cross-coupling 7 and acetophenone transfer hydrogenation. 8 Nonsymmetric iminophosphonamines bearing different N,N′-substituents have been efficiently utilized in the Kumada cross-coupling of aryl Grignard reagents with aryl chlorides and fluorides 9 and in controlling regio-and stereoselectivity in the polymerization of isoprene.…”

Section: Isolated Yields 58-80% In One Potmentioning

confidence: 99%

Synthesis of Nonsymmetric Iminophosphonamines by Kirsanov Condensation

Peganova¹,

Kalsin

2019

Synthesis

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Despite the growing interest in iminophosphonamines R2P(NHR′)(NR′), nonsymmetric examples bearing different N,N′-substituents are quite rare and have been prepared exclusively by the Staudinger reaction. We report here the synthesis of a series of new iminophosphonamines Ph2P(NHR)(NR′) (R = Me, t-Bu, o-Tol; R′ = p-Tol, o-Tol, 2,6-Xyl, 2,6-Diip, p-Ts) showing that the Kirsanov condensation is a viable and simpler approach, although with some limitations. This method allows the synthesis to be accomplished in a one-pot manner via stepwise double amination of a trihalophosphorane and permits the introduction of at least one sterically bulky N-substituent. The second amination step is shown to be highly sensitive to: (a) the steric bulk of the amine, and (b) the acidity of the aminohalophosphonium intermediate.

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“…Recently, we have reported on the synthesis of complexes of platinum metals with an anionic κ 2 - N , N iminophosphonamide ligand [R 2 P(NR′) 2 ] − (NPN), particularly of palladium, platinum, − and ruthenium (Ru). − In contrast to structurally similar amidinate ligand (NCN), the NPN ligand is zwitterionic and can act as a strong donor with two nitrogen (N) atoms bearing full negative charges, donating either 4σ or 4σ,2π electrons to a metal atom. , Due to these features, the NPN ligand is not a spectator ligand. Rather, it can assist transformations in the metal coordination sphere or even actively participate in them, as we have demonstrated for half-sandwich arene Ru NPNs. , Thus, 16e̅ Ru NPN complexes with N-alkyl substituents readily react with CO to give carbamoyl products, in which CO was inserted into the Ru–N bond .…”

Section: Introductionmentioning

confidence: 99%

Versatile Reactivity of Half-Sandwich Rhodium(III) Iminophosphonamide Complexes

et al. 2022

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Novel 18e̅ and 16e̅ pentamethylcyclopentadienyl rhodium(III) complexes [(η5-C5Me5)RhX(NPN)] (1a,b, X = Cl; 2a–c, X = PF6, BAr4 F) with chelating zwitterionic iminophosphonamide (NPN) ligands (Ph2P(NR)(NR′); a, R = R′ = p-Tol; b, R = p-Tol, R′ = Me; c, R = R′ = Me) were synthesized and characterized by single-crystal X-ray diffraction. In the 16e̅ complexes 2, the rhodium (Rh) atom is efficiently stabilized by π-donation of unshared N electrons, thus hampering coordination of the external ligands and rendering the 18e̅ complexes labile. Due to low coordination enthalpy, the cationic 18e̅ monocarbonyl and pyridine adducts 2a·L are stable only at low temperatures. At room temperature, 2·CO adducts readily give stable carbonyl–carbamoyl complexes [(η5-C5Me5)Rh(CO){(CO(NR′)Ph2P(NR)}]+ (4) formed as a result of CO insertion into the Rh–N bond, thus showing high nucleophilicity of the N atoms in 18e̅ complexes. High basicity of the Na+NPN– precursors caused side deprotonation of the η5-C5Me5 ligand during the synthesis of 1 that yields unstable fulvene Rh(I) complexes [(η4-C5Me4CH2)Rh{Ph2P(NR)(NR′)2}] (3a,b). Complex 3a undergoes a facile reaction with isoprene to yield an unusual [(η5:η1-C5Me4(CH2)C(Me)CHCH2)Rh(NPN)] complexthe first example of intermolecular 1,4-metallacycloaddition of diene to the Rh–fulvene complex.

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Palladium(II) aminoiminophosphoranate complexes as cross-coupling catalysts

Cited by 9 publications

References 49 publications

π-Allylpalladium Complexes in Synthesis: An Update

π-Allylpalladium Complexes in Synthesis: An Update

Synthesis of Nonsymmetric Iminophosphonamines by Kirsanov Condensation

Versatile Reactivity of Half-Sandwich Rhodium(III) Iminophosphonamide Complexes

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