Silver-catalyzed furoquinolines synthesis: from nitrogen effects to the use of silver imidazolatepolymer as a new and robust silver catalyst

Parker, Evelyne; Leconte, Nicolas; Godet, Thomas; Belmont, Philippe

doi:10.1039/c0cc02623a

Cited by 40 publications

(15 citation statements)

References 39 publications

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“…(4), Ru(1)ÀN(2) 2.136(4), Ru(1)ÀP(1) 2.2482 (12), Ru(1)ÀP(2) 2.2604 (13), Ru(1)ÀCl(1) 2.5077(11), Ru(1)ÀCl(2) 2.4982(11);N(1)-Ru(1)-N(2) 175.27 (13), P(1)-Ru(1)-Cl(1) 168.95(4), P(2)-Ru(1)-Cl(2) 170.02 (4), N(1)-Ru(1)-P(1)83.49 (10), N(2)-Ru(1)-P(1) 94.35 (10),N(1)-Ru(1)-P(2)92. 28(11), N(2)-Ru(1)-P(2)83.76(10), P(1)-Ru(1)-P(2) 96.31 (5), N(1)-Ru(1)-Cl(2) 93.94 (10), N(2)-Ru(1)-Cl(2)90.34(10), P(1)-Ru(1)-Cl(2) 92.16 (5), N(1)-Ru(1)-Cl(1) 90.53 (10), N(2)-Ru(1)-Cl(1)92.26(10), P(2)-Ru(1)-Cl(1) 93.20 (5), Cl(2)-Ru(1)-Cl(1) 78.95(4), Ru(1)-Cl(1)-Ru(1A) 100.79(6), Ru(1)-Cl(2)-Ru(1A)1 01. 31(6).…”

Section: Resultsunclassified

“…The resultso btained above naturallyr aise the question about what factorsa re responsible for the different reactivity of the oxacyclocarbene intermediates in the catalytic reactions, in particular the marked difference between 12 and 12'.I nitial- (3), Ru(1)ÀN(1) 2.194 (2), Ru(1)ÀN(2)2.203 (2), Ru(1)ÀP(2) 2.2764(9), Ru(1)ÀP(1) 2.2833 (14), Ru(1)ÀCl(1) 2.4540 (13), O(1)ÀC(1) 1.321 (4), O(1)ÀC(6) 1.466 (4), C(1)ÀC(2) 1.498 (4), C(2)ÀC(3) 1.538 (5),C (3)ÀC(4) 1.522(6), C(4)ÀC (5) 1.509(6), C(5)ÀC(6) 1.504(6);C (1)-Ru(1)-N(1) 91.16(11), C(1)-Ru(1)-N(2) 170.39 (10), N(1)-Ru(1)-N(2) 92.49(9), C(1)-Ru(1)-P(2) 93.93(9), N(1)-Ru(1)-P(2) 174. 78(6), N(2)-Ru(1)-P(2) 82.30 (7), N(1)-Ru(1)-P(1) 80.29 (7), N(2)-Ru(1)-P(1) 94.50 (7), P(2)-Ru(1)-P(1) 100.36 (4), N(1)-Ru(1)-Cl(1)89.25 (7), N(2)-Ru(1)-Cl(1) 80.99 (7), P(2)-Ru(1)-Cl(1) 89.62 (4),P (1)-Ru(1)-Cl(1) 168.45 (3).…”

Section: Mechanistic Studymentioning

confidence: 99%

“…78(6), N(2)-Ru(1)-P(2) 82.30 (7), N(1)-Ru(1)-P(1) 80.29 (7), N(2)-Ru(1)-P(1) 94.50 (7), P(2)-Ru(1)-P(1) 100.36 (4), N(1)-Ru(1)-Cl(1)89.25 (7), N(2)-Ru(1)-Cl(1) 80.99 (7), P(2)-Ru(1)-Cl(1) 89.62 (4),P (1)-Ru(1)-Cl(1) 168.45 (3). (5), Ru(1)ÀN(1) 2.210 (3), Ru(1)ÀN(2)2.212(4), Ru(1)ÀP(2) 2.2844 (12), Ru(1)ÀP(1) 2.2915 (15), Ru(1)ÀCl(1) 2.4694 (15), O(1)ÀC(1) 1.292(6), O(1)ÀC(5) 1.467 (7), C(1)ÀC(2) 1.491 (7), C(2)ÀC(3) 1.413 (10),C (3)ÀC(4) 1.403 (12), C(4)À C(5) 1.402 (12); C(1)-Ru(1)-N(1) 93.39(17), C(1)-Ru(1)-N(2) 173.49(17),N (1)-Ru(1)-N(2) 89.16 (13), C(1)-Ru(1)-P (2) 94.89(14), N(1)-Ru(1)-P(2) 171.70 (10), N(2)-Ru(1)-P(2) 82.67 (10),N (1)-Ru(1)-P(1)81.57 (10), N(2)-Ru(1)-P(1) 95.48 (10), P(2)-Ru(1)-P(1) 97.69 (5), N(1)-Ru(1)-Cl(1) 87.06 (10), N(2)-Ru(1)-Cl(1)83.47 (10), P(2)-Ru(1)-Cl(1) 93.45(4),P (1)-Ru(1)-Cl(1) 168.60(4). (4), Ru(1)ÀN(1) 2.187 (3), Ru(1)ÀN (2)2.215(3), Ru(1)ÀP (2) 2.2993 (10), Ru(1)ÀP(1) 2.2903(11), Ru(1)ÀCl(1) 2.4480(11), O(1)ÀC(1) 1.319 (5), O(1)ÀC (4) 1.477 (5), C(1)ÀC(2) 1.512 (5), C(2)ÀC(3) 1.523(6),C(3)ÀC(4) 1.506(8);C(1)-Ru(1)-N(1) 87.46 (14), C(1)-Ru(1)-N(2) 179.45 (14), N(1)-Ru(1)-N(2) 92.93(11), C(1)-Ru(1)-P(2) 98.16 (12),N (1)-Ru(1)-P(2)174.34(8), N(2)-Ru(1)-P(2) 81.45(8), N(1)-Ru(1)-P(1) 81.17(8), N(2)-Ru(1)-P(1) 88.66(8), P(2)-Ru(1)-P(1) 99.…”

Section: Mechanistic Studyunclassified

“…[2,3] The catalytic cycloisomerization of alkynols represents an atom-economic pathway to afford cyclic enol ethers, which are very useful synthetic intermediates in the construction of diverse oxygen-containing heterocycles. [4] Various transition metals like molybdenum, [5] tungsten, [6] copper, [7] palladium, [8] platinum, [9] silver, [10] gold, [11] ruthenium, [12] rhodium, [13] and osmium [14] have been explored as catalysts for these cycloisomerization reactions. In general, molybdenum, tungsten, ruthenium,o smium, and rhodium systems were proposed to proceed through intramolecular nucleophilic addition of the hydroxyl group to at ransition metal vinylidenei ntermediate, whereas copper, gold, platinum, andp alladium systems were proposed to proceed throughh ydroxyl group addi-tion to one carbon of a h 2 -alkyne intermediate.…”

Section: Introductionmentioning

confidence: 99%

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Efficient endo Cycloisomerization of Terminal Alkynols Catalyzed by a New Ruthenium Complex with 8‐(Diphenylphosphino)quinoline Ligand and Mechanistic Investigation

Cai

et al. 2018

Chemistry A European J

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Several new ruthenium complexes supported by the P,N-donor ligand 8-(diphenylphosphino)quinoline (DPPQ) were synthesized, including [RuCl (DPPQ) ] (1), [Ru(μ-Cl)(DPPQ) ] (BPh ) (2), and [RuCl(DPPQ) Py](BF ) (3). Complex 2, with only 1 mol % loading, was found to be catalytically active for the endo cycloisomerization of various terminal alkynols to endo-cyclic enol ethers in moderate to excellent yields. In particular, the 7- and 8-endo heterocyclization can be achieved efficiently to give the seven-membered 3-benzoxepine and eight-membered 3-benzo[d]oxocine derivatives. The stoichiometric reactions of 2 with various alkynol substrates have been carried out to investigate the mechanism, which led to a series of seven-, six-, and five-membered oxacyclocarbene ruthenium complexes including [RuCl(DPPQ) {=CCH C H CH CH O}](BPh ) (12) and [RuCl(DPPQ) {=CCH (CH ) CH O}](BPh ) (n=3, 12'; n=2, 13; n=1, 14). The quantitative transformation of oxacyclocarbene 12 into catalyst 2 and 3-benzoxepine 5 a as well as the efficient catalytic activity of 12 for the endo-cyclization of 2-(2-ethynylphenyl)ethanol (4 a) demonstrated that 12 is a key intermediate involved in the catalytic cycle. Moreover, comparative studies on the modeling reactions and catalytic activity of the series of oxacyclocarbene complexes indicated that the different catalytic activity of 2 for the endo-cycloisomerization of different types of alkynols can be related to the reactivity of the respective ruthenium oxacyclocarbene intermediates.

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Section: Resultsunclassified

Section: Mechanistic Studymentioning

confidence: 99%

Section: Mechanistic Studyunclassified

Section: Introductionmentioning

confidence: 99%

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Efficient endo Cycloisomerization of Terminal Alkynols Catalyzed by a New Ruthenium Complex with 8‐(Diphenylphosphino)quinoline Ligand and Mechanistic Investigation

Cai

et al. 2018

Chemistry A European J

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“…2-Alkynylbenzaldehyde 2 [58–59] was chosen as the first model substrate for a cyclization reaction in the presence of methanol as a second nucleophile. This tandem addition/cycloisomerization was previously described in high yields (>95%) using 5 mol % catalyst loadings starting from 2-(alkynyl)quinoline-3-carbaldehyde [60–61] with AgOTf catalyst and starting from 2-alkynylbenzaldehyde derivatives [62] in the presence of a macrocyclic pyridine-tetraaza complex of Ag(I) as a catalyst. In our control experiment, alkyne 2 was converted into product 4 in high yield (88 %) using AgOTf at 5 mol % (Table 1, entry 1).…”

Section: Resultsmentioning

confidence: 99%

Self-assembled coordination thioether silver(I) macrocyclic complexes for homogeneous catalysis

Cao

Lacoudre

Rossy

et al. 2019

Beilstein J. Org. Chem.

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The bis-ortho-thioether 9,10-bis[(o-methylthio)phenyl]anthracene was synthesized as a syn-atropisomer, as revealed by X-ray diffraction. This alkylaryl thioether ligand (L) formed different macrocyclic complexes by coordination with silver(I) salts depending on the nature of the anion: M2L2 for AgOTf and AgOTFA, M6L4 for AgNO3. A discrete M2L complex was obtained in the presence of bulky PPh3AgOTf. These silver(I) complexes adopted similar structures in solution and in the solid state. As each sulfur atom in the ligand is prochiral, macrocycles L2M2 were obtained as mixtures of diastereoisomers, depending on the configurations of the sulfur atoms coordinated to silver cations. The X-ray structures of the two L2·(AgOTf)2 stereoisomers highlighted their different geometry. The catalytic activity of all silver(I) complexes was effective under homogeneous conditions in two tandem addition/cycloisomerization of alkynes using 0.5–1 mol % of catalytic loading.

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Silver(I) Imidazolate

Rae¹,

Belmont

2013

Encyclopedia of Reagents for Organic Synthesis

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Silver-catalyzed furoquinolines synthesis: from nitrogen effects to the use of silver imidazolatepolymer as a new and robust silver catalyst

Cited by 40 publications

References 39 publications

Efficient endo Cycloisomerization of Terminal Alkynols Catalyzed by a New Ruthenium Complex with 8‐(Diphenylphosphino)quinoline Ligand and Mechanistic Investigation

Efficient endo Cycloisomerization of Terminal Alkynols Catalyzed by a New Ruthenium Complex with 8‐(Diphenylphosphino)quinoline Ligand and Mechanistic Investigation

Self-assembled coordination thioether silver(I) macrocyclic complexes for homogeneous catalysis

Silver(I) Imidazolate

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