Syntheses of Thieno[2,3-c]-, Pyrrolo[2,3-c]- and Indolo[2,3-c]diazanaphthalenes by Photocyclization of Acylaminopyridines

We present results on the amidation of aryl halides and sulfonates utilizing a monodentate biaryl phosphine-Pd catalyst. Our results are in accord with a previous report that suggests that the formation of kappa(2)-amidate complexes is deleterious to the effectiveness of a catalyst for this transformation and that their formation can be prevented by the use of appropriate bidentate ligands. We now provide data that suggest that the use of certain monodentate ligands can also prevent the formation of the kappa(2)-amidate complexes and thereby generate more stable catalysts for the amination of aryl chlorides. Furthermore, computational studies shed light on the importance of the key feature(s) of the biaryl phosphines (a methyl group ortho to the phosphorus center) that enable the coupling to occur. The use of ligands that possess a methyl group ortho to the phosphorus center allows a variety of aryl and heteroaryl chlorides with various amides to be coupled in high yield.

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“…[28] 3, Entry 4). [29] Using the general procedure, 3, Entry 6). [30] Using the general procedure, 6-chloroquinoline 4, Entry 1).…”

mentioning

confidence: 99%

Pd-Catalyzed Amidations of Aryl Chlorides Using Monodentate Biaryl Phosphine Ligands: A Kinetic, Computational, and Synthetic Investigation

et al. 2007

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“…The general process of cyclization resulting from photoenolization is potentially useful and versatile and irradiation of the nonconjugated aryl-ethene 128 results in the formation of the exo and endo isomers of the intramolecular addition product 129. eX> o (134 ) cloalkenyl ring, and whereas the cyclohexene derivative gives the cyclized compound 133 in the presence of the Lewis acid, methanol, or trifluoroacetic acid, the cyclopentene system, both in the absence and presence of the acid catalyst, forms the spiro compound 134. (119) Yields in the presence of the acid catalyst from the latter system are, however, low.…”

Section: Aryl Enonesmentioning

confidence: 99%

Photoaddition and Photocyclization Processes of Aromatic Compounds

Gilbert

1984

Synthetic Organic Photochemistry

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Photocyclization of Stilbenes and Related Molecules

1984

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On irradiation in solution with ultraviolet (UV) light, cis ‐stilbene undergoes reversible photocyclization to give trans ‐4a,4b‐dihydrophenanthrene, an intermediate that can be trapped oxidatively with hydrogen acceptors such as iodine, oxygen, or tetracyanoethylene to give phenanthrene in high yield. This type of photoreaction occurs with a wide range of substituted stilbenes and related molecules, including various polycyclic and heterocyclic analogs; in addition, certain systems with a single heteroatom (nitrogen, oxygen, or sulfur) in place of the central π bond undergo photocyclization, creating a new five‐membered heterocyclic ring. In some of these photocyclizing systems, the transient dihydroaromatic intermediates are trapped without added oxidants by the elimination of suitable leaving groups or by various hydrogen shifts. Photocyclization is the preferred method for the synthesis of many different polynuclear aromatic systems. The discovery and early development of stilbene photocyclization has been surveyed, and several other general reviews have appeared.

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Syntheses of Thieno[2,3-c]-, Pyrrolo[2,3-c]- and Indolo[2,3-c]diazanaphthalenes by Photocyclization of Acylaminopyridines

Cited by 11 publications

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Pd-Catalyzed Amidations of Aryl Chlorides Using Monodentate Biaryl Phosphine Ligands: A Kinetic, Computational, and Synthetic Investigation

Pd-Catalyzed Amidations of Aryl Chlorides Using Monodentate Biaryl Phosphine Ligands: A Kinetic, Computational, and Synthetic Investigation

Photoaddition and Photocyclization Processes of Aromatic Compounds

Photocyclization of Stilbenes and Related Molecules

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