P‐Stereogenic Secondary Iminophosphorane Ligands and Their Rhodium(I) Complexes: Taking Advantage of NH/PH Tautomerism

León, Thierry; Parera, Magda; Roglans, Anna; Riéra, Antoni

doi:10.1002/ange.201201031

Cited by 23 publications

(10 citation statements)

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“…Thec hiral phosphoramidite ligand [14] L*1 worked well to give 2h in 95 %y ield and 62 % ee. Thec hiral MOP ligand [15] L*2,P -stereogenic iminophosphorane [16] L*3,a nd the planar-chiral phosphine-olefin ligand [17] L*4 were also used, as these compounds should act as hemilabile bidentate ligands.However,any improvements on the results were not observed. Nevertheless,t he result given by L*1 shows promising reactivity of nickel(0)/chiral monodentate phosphine systems in this first example of an ickel(0)-catalyzed asymmetric carbonylative cycloaddition of ene-imines and CO.F urther studies to attain higher enantioselectivity are currently ongoing.…”

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confidence: 99%

Efficient Synthesis of Polycyclic γ‐Lactams by Catalytic Carbonylation of Ene‐Imines via Nickelacycle Intermediates

et al. 2017

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The nickel(0)-catalyzed carbonylative cycloaddition of 1,5-and 1,6-ene-imines with carbon monoxide (CO) is reported. Keytothis reaction is the efficient regeneration of the catalytically active nickel(0) species from nickel carbonyl complexes such as [Ni(CO) 3 L].Avariety of tri-and tetracyclic g-lactams were thus prepared in excellent yields with 100 % atom efficiency.Preliminary results on asymmetric derivatives promise potential in the synthesis of enantioenriched polycyclic g-lactams.

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Efficient Synthesis of Polycyclic γ‐Lactams by Catalytic Carbonylation of Ene‐Imines via Nickelacycle Intermediates

et al. 2017

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“…Coordination of the oxygen atom leads to desymmetrization of the sulfonamide fragment and induces chirality at the sulfur atom. [15] The dimer has exact crystallographic C 2 symmetry with both sulfur atoms of equal chirality, but the unit cell possesses an inversion center as the complex crystallizes as a true racemate. The P1-Ru-P2 angle of 100.154 (15)°as well as the O1-Ru-C17 angle of 174.02(5)°exemplify the distorted-octahedral geometry around Ru.…”

Section: Coordination To a Ru II Precursor Bearing An Internal Basementioning

confidence: 99%

“…The Ru-N bond length varies from 1.9991(13) Å for the NCMe trans to the oxygen atom to 2.1248(13) Å for the NCMe trans to P, which follows the same trend as reported for related compounds. [17] There is slight out-of-plane bending of the two axial NCMe units away from the PNSO side, which might be related to slight steric hindrance [N2-Ru-N4 175.11(5) Å, Ru-N2-C20 174.81 (15)…”

Section: Substitution Reactions On Piano-stool Complexmentioning

confidence: 99%

“…Hydrogen atoms and PF 6 counterion and CH 2 Cl 2 solvent (for 11) have been omitted for clarity. Selected bond lengths [Å] and angles [°] for 11: Ru-P 2.2637(3), Ru-O1 2.1210(10), Ru-N2 2.0200(13), Ru-N3 1.9991(13), Ru-N4 2.0175(12), Ru-N5 2.1248(13), P-N1 1.6720(12), N1-S 1.5544(12), S-O1 1.4996(10), S-O2 1.4482(10); P-Ru-O1 83.87(3), P-Ru-N2 93.27(4), P-Ru-N3 96.87(4), P-Ru-N5 171.22(4), N2-Ru-N4 175.11(5), O1-Ru-N3 178.70(4), P-N1-S 116.65(7), N1-S-O1 112.65(6), N1-S-O2 112.05(6), Ru-O1-S 117.44(6), Ru-N2-C20 174.81(15). For 13: Ru-P 2.3230(6), Ru-O1 2.1334(16), Ru-N2 2.0112(19), P-N1 1.671(2), N1-S 1.552(2), S-O1 1.4978(18), S-O2 1.4387(19); P-Ru-O1 81.31(5), P-Ru-N2 90.41(6), PЈ-Ru-O1 98.69(5), O1-Ru-N2 89.55(7), P-N1-S 115.40(13), N1-S-O1 113.36(11), N1-S-O2 113.00(12), Ru-O1-S 118.55(9).…”

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Synthesis, Coordination Chemistry, and Cooperative Activation of H₂ with Ruthenium Complexes of Proton‐Responsive METAMORPhos Ligands

et al. 2013

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The synthetic scope of proton-responsive sulfonamidophosphorus (METAMORPhos) ligands is expanded and design principles for the selective formation of particular tautomers, ion pairs, or double condensation products are elucidated. These systems have been introduced in the coordination sphere of Ru for the first time, thereby enabling the exclusive coordination as a monoanionic P,O chelate. Depending on the Ru precursor, halide-bridged dinuclear species 3-5 or cymene-derived piano-stool complexes 6-9 are isolated. The METAMORPhos framework is shown to play a role in the heterolytic cleavage of H 2 , with species 7 converted into neu- [a] van '1826 tral monohydride 10. Substitution chemistry with cymene complex 7 has also been examined, thereby giving rise to tetrakis(acetonitrile) adduct 11. Introduction of a second equivalent of METAMORPhos ligand to this species yielded the bis(ligated) derivative 13, for which variable-temperature (VT) NMR spectroscopy indicates coalescence of the phosphine donors at high temperature. Solid-state structures of 3, 6, 11, and 13 are presented to establish the precise bonding situation of the inorganic PNSO framework within METAMORPhos upon coordination as a proton-responsive monoanionic P,O chelate.

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“…We have evaluated both methodologically and mechanistically the [2+2+2] cycloaddition reaction as an efficient entry to tetracycles by the reaction of mac-rocyclic substrates, [14] and to tricyclic skeletons starting from linear triunsaturated substrates. [15] Our interest in the construction of topologically new polycyclic structures, prompted us to explore the [2+2+2] cycloaddition reaction of linear alleneene-allene and allene-yne-allene derivatives. Here we describe the synthesis of the substrates, its [2+2+2] cycloaddition reaction to furnish tricyclic diene scaffolds, and the subsequent Diels-Alder reaction efficiently affording pentacyclic compounds.…”

Section: Introductionmentioning

confidence: 99%

Stereoselective Rhodium‐Catalysed [2+2+2] Cycloaddition of Linear Allene–Ene/Yne–Allene Substrates: Reactivity and Theoretical Mechanistic Studies

Haraburda

Torres

Parella

et al. 2014

Chemistry A European J

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Allene-ene-allene (2 and 5) and allene-yne-allene (3 and 7) N-tosyl and O-linked substrates were satisfactorily synthesised. The [2+2+2] cycloaddition reaction catalysed by the Wilkinson catalyst [RhCl(PPh3 )3 ] was evaluated. Substrates 2 and 5, which bear a double bond in the central position, gave a tricyclic structure in a reaction in which four contiguous stereogenic centres were formed as a single diastereomer. The reaction of substrates 3 and 7, which bear a triple bond in the central position, gave a tricyclic structure with a cyclohexenic ring core, again in a diastereoselective manner. All cycloadducts were formed by a regioselective reaction of the inner allene double bond and, therefore, feature an exocyclic diene motif. A Diels-Alder reaction on N-tosyl linked cycloadducts 8 and 10 allowed pentacyclic scaffolds to be diastereoselectively constructed. The reactivity of the allenes on [2+2+2] cycloaddition reactions was studied for the first time by density functional theory calculations. This mechanistic study rationalizes the order in which the unsaturations take part in the catalytic cycle, the reactivity of the two double bonds of the allene towards the [2+2+2] cycloaddition reaction, and the diastereoselectivity of the reaction.

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P‐Stereogenic Secondary Iminophosphorane Ligands and Their Rhodium(I) Complexes: Taking Advantage of NH/PH Tautomerism

Cited by 23 publications

References 55 publications

Efficient Synthesis of Polycyclic γ‐Lactams by Catalytic Carbonylation of Ene‐Imines via Nickelacycle Intermediates

Efficient Synthesis of Polycyclic γ‐Lactams by Catalytic Carbonylation of Ene‐Imines via Nickelacycle Intermediates

Synthesis, Coordination Chemistry, and Cooperative Activation of H₂ with Ruthenium Complexes of Proton‐Responsive METAMORPhos Ligands

Stereoselective Rhodium‐Catalysed [2+2+2] Cycloaddition of Linear Allene–Ene/Yne–Allene Substrates: Reactivity and Theoretical Mechanistic Studies

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P‐Stereogenic Secondary Iminophosphorane Ligands and Their Rhodium(I) Complexes: Taking Advantage of NH/PH Tautomerism

Cited by 23 publications

References 55 publications

Efficient Synthesis of Polycyclic γ‐Lactams by Catalytic Carbonylation of Ene‐Imines via Nickelacycle Intermediates

Efficient Synthesis of Polycyclic γ‐Lactams by Catalytic Carbonylation of Ene‐Imines via Nickelacycle Intermediates

Synthesis, Coordination Chemistry, and Cooperative Activation of H2 with Ruthenium Complexes of Proton‐Responsive METAMORPhos Ligands

Stereoselective Rhodium‐Catalysed [2+2+2] Cycloaddition of Linear Allene–Ene/Yne–Allene Substrates: Reactivity and Theoretical Mechanistic Studies

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Synthesis, Coordination Chemistry, and Cooperative Activation of H₂ with Ruthenium Complexes of Proton‐Responsive METAMORPhos Ligands