A competitive and highly selective 7-, 6- and 5-annulation with 1,3-migration through C–H and N–H – alkyne coupling

Ajarul, Sk; Kayet, Anirban; Pati, Tanmay K.; Maiti, Dilip K.

doi:10.1039/c9cc07360d

Cited by 9 publications

(4 citation statements)

References 44 publications

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“…Instead, a rearrangement of the fluorous acyl moiety to the compound 17a was observed (Scheme 3). The 1,3-acyl shift in the cyclization of alkynylated anilines to form 3-acylindoles was reported in literature but could so far, to the best of our knowledge, only be achieved thermally in the presence of metals like platinum, 34,35 zinc 36 and palladium 37 , like exemplarily shown on Scheme 1b for the platinum catalysed cyclization of 7 to the 3-acylindole derivative 8. Scheme 3.…”

Section: Resultsmentioning

confidence: 86%

F-tag induced acyl shift in the photochemical cyclization of o-alkynylated N-alkyl-N-acylamides to indoles

Jung

Bräse

Šimek

et al. 2022

Preprint

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A photochemical cyclization of F-tagged, o-alkynylated N-alkylamides to indoles catalyzed by the [Ir(dtbbpy)(ppy)2]PF6 is presented. This straightforward and efficient reaction involves an intramolecular rearrangement due to the presence of fluorine in the acyl moiety and is the first example of photochemically induced 1,3-acyl shift in the cyclization towards 3-acylidoles. A four-step reaction sequence to the desired derivatives including the photoreaction as a key step has been developed and optimized. The compatibility of differently substituted F-tagged precursors with the photocyclization step was investigated and the robustness of this step towards modifications could be shown. In total, 19 so far unknown derivatives with diverse modifications in positions N1 and C2 were synthesized in very good yields and fully characterized.

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Section: Resultsmentioning

confidence: 86%

F-tag induced acyl shift in the photochemical cyclization of o-alkynylated N-alkyl-N-acylamides to indoles

Jung

Bräse

Šimek

et al. 2022

Preprint

View full text Add to dashboard Cite

show abstract

“…Instead, a rearrangement of the fluorous acyl moiety to the compound 17 a was observed (Scheme 3). The 1,3-acyl shift in the cyclization of alkynylated anilines to form 3-acylindoles was reported in literature but could so far, to the best of our knowledge, only be achieved thermally in the presence of metals like platinum, [21,22] zinc [23] and palladium, [24] like exemplarily shown on Scheme 1b for the platinum catalysed cyclization of 7 to the 3-acylindole derivative 8.…”

Section: Resultsmentioning

confidence: 90%

F‐Tag Induced Acyl Shift in the Photochemical Cyclization of o‐Alkynylated N‐Alkyl‐N‐acylamides to Indoles**

et al. 2023

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A photochemical cyclization of F‐tagged, o‐alkynylated N‐alkylamides to indoles catalyzed by [Ir(dF(CF3)ppy)2(dtbpy)]PF6 is presented. This straightforward and efficient reaction involves an intramolecular rearrangement due to the presence of an electron withdrawing group in the acyl moiety and is the first example of photochemically induced 1,3‐acyl shift in the cyclization towards 3‐acylindoles. A four‐step reaction sequence including the photoreaction as a key step to the desired indoles has been developed and optimized. The compatibility of differently substituted F‐tagged precursors with the photocyclization step was investigated and the robustness of this step towards modifications could be shown. In total, 16 so far unknown derivatives with diverse modifications in positions N1 and C2, bearing a pentadecafluorooctanoyl moiety as F‐tag, were synthesized in very good yields and fully characterized.

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“…3‐Oxo‐3‐phenyl‐N‐(2‐(phenylethynyl)phenyl)propanamide 215 was employed as the starting substrate (Scheme 59). [67] The starting material 3‐oxo‐3‐phenyl‐N‐(2‐(phenylethynyl)phenyl)propanamide 215 is synthesized by the reaction between 2‐(phenylethynyl)aniline and ethyl benzoyl acetate at reflux temperature in toluene. Upon increasing the loading of the ZnCl 2 catalyst from 10 to 20 mol%, an excellent yield of 216 was achieved along with the subsidized by‐product.…”

Section: Miscellaneous Metal‐catalyzed Approachesmentioning

confidence: 99%

Metal‐Catalyzed Approaches for the Construction of Azepinones

et al. 2022

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The azepinone scaffolds are an important framework of pharmaceutically interesting compounds and many bioactive natural products. This review mainly focused on the metalcatalyzed approaches towards the synthesis of azepinones . Mainly it covers cycloisomerization and metal carbenoid insertion. It also involves transformations through cycloaddition reactions, metathesis reactions, microwave reactions and direct CÀ H/CÀ C/CÀ N activation reactions. The applications, substrate scope, limitations and plausible mechanisms of these transformations have also been discussed.

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A competitive and highly selective 7-, 6- and 5-annulation with 1,3-migration through C–H and N–H – alkyne coupling

Abstract: A highly competitive and selective C–C and N–C cross-coupled 7-, 6- and 5-annulation of 2-ethynylanilides furnished 1H-benzo[b]azepin-2(5H)-ones, 2-quinolinones, and 3-acylindoles, respectively using smart catalyst ZnCl2 or I2 through 1,3-migration.

Cited by 9 publications

References 44 publications

F-tag induced acyl shift in the photochemical cyclization of o-alkynylated N-alkyl-N-acylamides to indoles

F-tag induced acyl shift in the photochemical cyclization of o-alkynylated N-alkyl-N-acylamides to indoles

F‐Tag Induced Acyl Shift in the Photochemical Cyclization of o‐Alkynylated N‐Alkyl‐N‐acylamides to Indoles**

Metal‐Catalyzed Approaches for the Construction of Azepinones

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