Rhodium(<scp>II</scp>)‐Catalyzed [4+3] Cyclization of Triazoles with Indole Derivatives and Its Application in the Total Synthesis of (±)‐Aurantioclavine

Duan, Shengguo; Xue, Bing; Meng, Huan; Ye, Zihang; Xu, Zefeng; Li, Chuan‐Ying

doi:10.1002/cjoc.202000657

Cited by 23 publications

(8 citation statements)

References 46 publications

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“…Recently, Li and co-workers 290 developed a Rh-catalyzed [4 + 3] cyclization of triazoles with various indole derivatives. They exploited this strategy in the total synthesis of the azepinoindole alkaloid (±)-aurantioclavine (198.6) In 2014, Yang and co-workers reported the stereoselective synthesis of oxaspirocycles from N-sulfonyl-1,2,3-triazoles (Scheme 149).…”

Section: Applications In Total Syntheses Of Natural Productsmentioning

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: Applications In Total Syntheses Of Natural Productsmentioning

confidence: 99%

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

2022

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“…In 2021, Li and co-workers performed a rhodium (II)catalyzed [4 + 3] cyclization between indole derivatives and triazoles in their synthesis of (�)-aurantioclavine (�)-1 (Scheme 9). [19] The [4 + 3] cyclization of NÀ H unprotected indole derivative 45 with triazole 46 under Rh 2 (piv) 4 catalysis and subsequent treatment with pyridinium p-toluenesulfonate (PPES) yielded tricyclic compound 47 with a yield of 61 %. The reduction of the double bond and the hydrazinolysis of the phthalimide were implemented in one step using N 2 H 4 * H 2 O, resulting in the corresponding primary amine product 48 in 69 % yield.…”

Section: Total and Formal Syntheses Via 4-substituted Tryptamine/tryp...mentioning

confidence: 99%

Efforts and Strategies for the Syntheses of Clavine‐Type Ergot Alkaloid Aurantioclavine

Jiang

et al. 2022

Eur J Org Chem

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Aurantioclavine, isolated by Kozlovskii from Penicillium aurantiovirens, is a unique member of the 3,4‐disubstituted indole alkaloids distinguished by an azepino[5,4,3‐cd]indole. As an essential intermediate in the biosynthesis of the complex polycyclic alkaloids of the fungal communesin, it has attracted considerable attention as a synthetic target. The development of various synthetic strategies for their application in total synthesis has been described. An overview focused on the synthesis of aurantioclavine from its first synthesis to the most recent one is present.

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“…Thus, the introduction of S and Se atoms into molecules has emerged as one of the most important strategies for the development of new functional molecules, such as catalysts, 1 pharmaceuticals, 2 fragrances, 3 food ingredients, 4 and photoelectric materials, 5 and has attracted more and more attention over the past several decades. Carbene is a highly important reactive intermediate in synthetic chemistry because it is widely used in a variety of reactions, 6,7 including cyclopropanation, X–H (X = C, O, N, S, Se, etc. ) insertion, 8 and ylide formation/rearrangement reactions.…”

Section: Introductionmentioning

confidence: 99%