Intramolecular Palladium‐Catalyzed Direct Arylation <i>vs.</i> Heck Reactions: Synthesis of Pyrroloisoquinolines and Isoindoles

Lage, Sergio; Martínez‐Estíbalez, Unai; Sotomayor, Nuria; Lete, Esther

doi:10.1002/adsc.200900368

Cited by 42 publications

(38 citation statements)

References 79 publications

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“…N-(o-Iodobenzyl)pyrroles 2c and 2d were obtained in high yields as a single E diastereomer, but 2b was obtained as a diastereomer mixture (E/Z, 1.1:1), which could not be separated by usual chromatographic methods (see Table 1). [23] Scheme 1. We first studied the carbolithiation reactions of N-(oiodobenzyl)pyrrole (2a) with tBuLi/TMEDA [(N,N,NЈ,NЈtetramethyl-1,2-ethylenediamine), see Scheme 2 and Table 2], starting from the previously used conditions.…”

Section: Resultsmentioning

confidence: 99%

Intramolecular Carbolithiation Reactions in the Construction of Medium‐Sized Rings. Synthesis of Pyrroloisoquinolines, Benzazepines, and Benzazocines

et al. 2012

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Mesityllithium (MesLi) was found to be superior to butyllithium for the formation of aryllithium intermediates by iodine–lithium exchange. Subsequent intramolecular carbolithiation of the 2‐alkenyl‐substituted ortho‐lithiated N‐benzylpyrroles proceeded efficiently when the alkene was substituted with an electron‐withdrawing group. The procedure is applicable to the construction of six‐, seven‐, and eight‐membered rings, thus, opening new routes to pyrroloisoquinolines, benzazepines, and benzazocines. Although the use of (–)‐sparteine as a chiral ligand led to low levels of enantioselection, enantiomerically pure isoquinolines could be synthesized by applying this protocol to the related pyrrolidines derived from proline, as the reactions proceeded with complete diastereoselectivity.

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Section: Resultsmentioning

confidence: 99%

Intramolecular Carbolithiation Reactions in the Construction of Medium‐Sized Rings. Synthesis of Pyrroloisoquinolines, Benzazepines, and Benzazocines

et al. 2012

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“…This is certainly due to the possible competitive Heck reaction with such substrates. [8][9][10][11] Heck reactions with benzalacetone, cinnamates or chalcone, proceed nicely. [12][13][14] Moreover, an example of Heck type reaction of 3-thiophen-3-ylacrylamide with iodobenzene has been described by Park and co-workers (Scheme 1, top).…”

Section: Introductionmentioning

confidence: 94%

Palladium-acetate catalyst for regioselective direct arylation at C2 of 3-furanyl or 3-thiophenyl acrylates with inhibition of Heck type reaction

et al. 2013

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. Palladium-acetate catalyst for regioselective direct arylation at C2 of 3-furanyl or 3-thiophenyl acrylates with inhibition of Heck type reaction. Tetrahedron, Elsevier, 2013, 69 (22) Abstract: Pd(OAc)2 / KOAc was found to be an efficient catalytic system for the direct arylation of thiophene and furan derivatives bearing an acrylate at C3. The selectivity of the reaction strongly depends on the nature of the coordinating base. Na2CO3 and Li2CO3 favours the Heck type reaction; whereas the use of KOAc or CsOAc promotes regioselective arylation at C2 of the heteroarene and inhibits the Heck type reaction. The direct arylation products were obtained in moderate to good yields using only 0.1 mol% of catalyst. Electron-withdrawing substituent on aryl bromide such as acetyl, formyl, ester, nitrile or nitro, favours the reaction; whereas electron-donating ones are unfavourable.

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“…In fact, when Bu 4 NCl was used instead of Bu 4 NOAc, the arylation reaction was not selective and gave variable yields of Heck-type products 323 (Figure 45). [212] In the same year, Iwao and co-workers synthesized 1-dearyllamellarin D (327) through a reaction se-quence in which its synthetic precursor 326 was prepared in 89% yield by PdA C H T U N G T R E N N U N G (PPh 3 ) 4 …”

Section: Ascwiley-vchdementioning

confidence: 99%

“…[211] In 2009, Lete and co-workers synthesized pyrrolo-A C H T U N G T R E N N U N G [2,1-a]isoindoles 322a-d in excellent yields by site-selective Pd-catalyzed intramolecular arylation of 2-alk-A C H T U N G T R E N N U N G enyl-substituted N-(ortho-iodobenzyl)pyrroles 321a-d (Table 12). [212] The cyclization reactions were carried out in DMSO at 60 8C using 1.5 equiv. of Bu 4 NOAc as a source of acetate ions and two types of catalyst systems.…”

Section: Ascwiley-vchdementioning

confidence: 99%

Cross‐Coupling of Heteroarenes by CH Functionalization: Recent Progress towards Direct Arylation and Heteroarylation Reactions Involving Heteroarenes Containing One Heteroatom

et al. 2014

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In recent years, transition metal-catalyzed direct (hetero)arylation reactions of heteroarenes with (hetero)aryl halides and pseudohalides have received significant attention as eco-friendly and economic alternatives to classical methods for the construction of heteroaryl-(hetero)aryl C À C bonds by transition metal-catalyzed cross-couplings involving the use of stoichiometric amounts of organometallic reagents. This critical review with 430 references covers the results obtained in the period January 2009 to February 2013 in the area of the transition metal-catalyzed direct inter-and intramolecular (hetero)arylation reactions of heteroarenes containing one heteroatom. Particular attention has been given to illustrate chemo-and site selectivity aspects of these reactions as well applications of these C À C bond forming reactions in the synthesis of pharmaceutically relevant compounds, natural products and their analogues and precursors. The most recent advancements into the mechanism(s) of these reactions have also been briefly reported.

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Intramolecular Palladium‐Catalyzed Direct Arylation vs. Heck Reactions: Synthesis of Pyrroloisoquinolines and Isoindoles

Cited by 42 publications

References 79 publications

Intramolecular Carbolithiation Reactions in the Construction of Medium‐Sized Rings. Synthesis of Pyrroloisoquinolines, Benzazepines, and Benzazocines

Intramolecular Carbolithiation Reactions in the Construction of Medium‐Sized Rings. Synthesis of Pyrroloisoquinolines, Benzazepines, and Benzazocines

Palladium-acetate catalyst for regioselective direct arylation at C2 of 3-furanyl or 3-thiophenyl acrylates with inhibition of Heck type reaction

Cross‐Coupling of Heteroarenes by CH Functionalization: Recent Progress towards Direct Arylation and Heteroarylation Reactions Involving Heteroarenes Containing One Heteroatom

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