Divergent Reactions between α‐Imino Rhodium Carbenoids and 1,3‐Diketones: Substrate‐Controlled O–H versus C–H Insertion

Mi, Pengbing; Yuan, Haiyan; Wang, Hannan; Liao, Peiqiu; Zhang, Jingping; Bi, Xihe

doi:10.1002/ejoc.201700009

Cited by 20 publications

(3 citation statements)

References 70 publications

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“…Similarly, Zhang and Bi disclosed substrate-controlled reactions of sulfonyltriazoles with 1,3-diketones to form pyrroles and fused pyrroles (Scheme ). Employment of acyclic symmetrical 1,3-diketones afforded polysubstituted pyrroles via O–H insertion- cum -condensation.…”

Section: Denitrogenative Transformations Of Triazolesmentioning

confidence: 99%

1,2,3-Triazole and Its Analogues: New Surrogates for Diazo Compounds

2022

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Readily accessible and shelf-stable 1,2,3-triazole and its analogues such as pyridotriazole, triazoloindole, benzotriazole, and thiadiazole exist in equilibrium with their ring-opened isomers, viz., diazo compounds. These ring-opened isomers could be trapped by various metal catalysts (e.g., Rh, Pd, Cu, Co, Ag, etc.) to generate the corresponding metal carbenoids with extrusion of nitrogen. As a consequence, these unique N-heterocycles facilitate access to a realm of N-containing complex structural motifs of biological importance through denitrogenative transformations such as transannulations, insertions, ylide formation, and rearrangements by trapping of the metal carbenoids with a diverse range of coupling partners (e.g., alkenes, alkynes, nitriles, carbo/heterocycles, X–H/C–X bonds, etc.). Hence, suitably substituted triazole derivatives have emerged as efficient surrogates of diazo compounds for the generation of reactive metal carbenoids during the past decades. In this comprehensive review, we aim to discuss in detail the remarkable advancement in their synthesis and synthetic applications.

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Section: Denitrogenative Transformations Of Triazolesmentioning

confidence: 99%

1,2,3-Triazole and Its Analogues: New Surrogates for Diazo Compounds

2022

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“…2H -Azirines 24 are prepared from isoxazoles 25 [ 33 ] or generated in situ from α -azidochalcones 26 [ 34 ]. The final example uses C-H insertion of α -imino rhodium carbenoids accessible from N -sulfonyl-1,2,3-triazoles 27 into 1,3-cyclohexanediones 8 [ 35 ].…”

Section: Synthesis Of 4567-tetrahydroindol-4-one Analogsmentioning

confidence: 99%

4,5,6,7-Tetrahydroindol-4-Ones as a Valuable Starting Point for the Synthesis of Polyheterocyclic Structures

Horsten¹,

Dehaen²

2021

Molecules

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This review focuses on the synthesis of polyheterocyclic structures with a variety of medicinal and optoelectronic applications, starting from readily available 4,5,6,7-tetrahydroindol-4-one analogs. First, routes toward the 4,5,6,7-tetrahydroindol-4-one starting materials are summarized, followed by synthetic pathways towards polyheterocyclic structures which are categorized based on the size and attachment point of the newly formed (hetero)cyclic ring.

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“…Up to now, the direct O‐H insertions of α‐imino rhodium carbenoids with proper substrates, taking benzylic alcohol for example, have been well studied. Moreover, some methods have been developed for the construction of nitrogen‐containing heterocycles (such as pyrrole skeleton) based on O−H insertion and subsequent rearrangement . With our continuing studies on the Rh II ‐catalyzed transformation of triazoles, we supposed this rhodium‐catalyzed O−H insertion/rearrangement strategy can be further applied to afford more attractive nitrogen‐containing heterocycles such as 3,4‐fused pyrroles by using Morita–Baylis–Hillman adducts as starting materials.…”

Section: Figurementioning

confidence: 99%

Rhodium(II)‐Catalyzed Reaction of 1‐Tosyl‐1,2,3‐triazoles with Morita–Baylis–Hillman Adducts: Synthesis of 3,4‐Fused Pyrroles

Jia

Jiang

Leng

et al. 2018

Chemistry An Asian Journal

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A cascade reaction of rhodium azavinylcarbenes with Morita-Baylis-Hillman (MBH) adducts enables a novel synthetic approach to 3,4-fused pyrroles. The cascade reaction begins with the insertion of O-H bond into rhodium azavinylcarbenes, subsquent sigmatropic rearrangement provides substituted α,β-unsaturated cyclic ketone intermediates. Then the intramolecular aza Michael addition/oxidative aromatization sequence give rise to a wide range of 3,4-fused pyrroles in good yields, and with excellent functional group compatibility.

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Divergent Reactions between α‐Imino Rhodium Carbenoids and 1,3‐Diketones: Substrate‐Controlled O–H versus C–H Insertion

Cited by 20 publications

References 70 publications

1,2,3-Triazole and Its Analogues: New Surrogates for Diazo Compounds

1,2,3-Triazole and Its Analogues: New Surrogates for Diazo Compounds

4,5,6,7-Tetrahydroindol-4-Ones as a Valuable Starting Point for the Synthesis of Polyheterocyclic Structures

Rhodium(II)‐Catalyzed Reaction of 1‐Tosyl‐1,2,3‐triazoles with Morita–Baylis–Hillman Adducts: Synthesis of 3,4‐Fused Pyrroles

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