Palladium‐Catalyzed Spirocyclization through C−H Activation and Regioselective Alkyne Insertion

Yoon, Hyung; Rölz, Martin; Landau, Felicitas; Lautens, Mark

doi:10.1002/ange.201706325

Cited by 40 publications

(6 citation statements)

References 54 publications

(22 reference statements)

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“…Recently, Lautens, Schoenebeck and co-workers reported the synthesis of spiro-fused heterocycles through an intramolecular Heck/C–H activation sequence using specific alkene-tethered aryl iodides (Fig. 1a ) 40 – 42 . Regarding the starting materials, those substrates might be preferably prepared through an initial palladium-catalyzed Tsuji-Trost allylation of 2-halophenols, which would provide a more efficient and step-economic way 43 – 45 .…”

Section: Resultsmentioning

confidence: 99%

“…Considering the versatility of the in-situ-generated palladacycles III 16 , 26 , 27 , subsequent functionalization including carbene and alkyne insertion should allow for the efficient construction of other classes of novel spiro compounds 29 , 30 , 41 , 42 . To demonstrate this synthetic potential, we performed the reaction of 1a and 2e with two equiv.…”

Section: Resultsmentioning

confidence: 99%

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The role of allyl ammonium salts in palladium-catalyzed cascade reactions towards the synthesis of spiro-fused heterocycles

Spannenberg

et al. 2020

Nat Commun

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There is a continuous need for designing new and improved synthetic methods aiming at minimizing reaction steps while increasing molecular complexity. In this respect, catalytic, one-pot cascade methodologies constitute an ideal tool for the construction of complex molecules with high chemo-, regio-, and stereoselectivity. Herein, we describe two general and efficient cascade procedures for the synthesis of spiro-fused heterocylces. This transformation combines selective nucleophilic substitution (SN2′), palladium-catalyzed Heck and C–H activation reactions in a cascade manner. The use of allylic ammonium salts and specific Pd catalysts are key to the success of the transformations. The synthetic utility of these methodologies is showcased by the preparation of 48 spiro-fused dihydrobenzofuranes and indolines including a variety of fluorinated derivatives.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

The role of allyl ammonium salts in palladium-catalyzed cascade reactions towards the synthesis of spiro-fused heterocycles

Spannenberg

et al. 2020

Nat Commun

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“…In 2017, Lautens et al reported the annulation reaction between aromatic acrylamides 66 and alkynes 68 to synthesize spirooxindoles 69 (Scheme 24a). 35 The effect of substituents on the substrate was examined. They observed that electron-deficient substituents such as fluoro provided better results than electron-rich substituents.…”

Section: Scheme 16 Rhodium Catalyzed Carboxylate-directed C-h Functio...mentioning

confidence: 99%

Reactivity of Alkynes with M-C Bonds generated through C-H Activation

Banjare

Mahulkar

Nanda

et al. 2022

Preprint

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Transition metal-catalyzed C-H activation and functionalization with various coupling partners is a well-explored area of research. Among the various coupling partners used, alkynes occupy a prominent position on account of their varied reactivity. Due to their low steric demand and a high degree of unsaturation they effectively overlap with metal d-orbitals and form multiple bond-forming events giving rise to complex skeletons that are otherwise challenging to synthesize. This makes alkyne one of the most successful coupling partners in terms of the number of useful transformations. Remarkably, by changing the reaction conditions and transition-metals from 5d to 3d, the behaviors of alkynes also change. Despite enormous explorations with alkynes, there are still a lot more possible ways by which alkynes can be made to react with M-C bonds generated through C-H activation. Especially with the development of new high and low valent first-row metal catalysts, there is plenty of scope for this chemistry to evolve as one of the most explored areas of research in coming years. Therefore, a review on this topic is both timely and useful for synthetic chemists who are working in this area. In this review, we have highlighted the diverse reactivity of alkynes with various transition metals and their applications along with some of our thoughts on future prospects.

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“…In 2017, the Lautens group reported a Pd‐catalyzed spirocyclization [Eq. (74‐1)] . This methodology gave access to a variety of spirooxindoles and spirodihydrobenzofurans 74.6 with excellent RR (>20:1).…”

Section: Carbon‐containing Nucleophilesmentioning

confidence: 99%

Tandem Reactions of Ynones: via Conjugate Addition of Nitrogen‐, Carbon‐, Oxygen‐, Boron‐, Silicon‐, Phosphorus‐, and Sulfur‐Containing Nucleophiles

et al. 2019

Adv Synth Catal

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Scheme 12. Enamines:T BAF-catalyzed cyclization.Scheme 13. Intramolecular cyclization.Scheme14. Intramolecular cyclizations.Scheme15. CÀNa nd OÀNb ond cleavage. Scheme 16. Applications of RNH-Nu. Scheme 17. NH-sulfoximines and NH-sulfondiimines. Scheme18. Radical cyclizationf or the synthesis of indoles. Scheme 22. 2H-Azirines:[3 + +2] cycloadditions. Scheme 23. Visible light-induced cycloaddition for pyrrole synthesis. Scheme24. Cyclization and sulfonyl migration. Scheme 25. NR 2 -E strategy analysis. Scheme 57. Several arenes for annulations. Scheme 58. Conjugateaddition. Scheme 59. Asymmetric conjugate addition.Scheme60. Conjugatea ddition andcyclization.

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Palladium‐Catalyzed Spirocyclization through C−H Activation and Regioselective Alkyne Insertion

Cited by 40 publications

References 54 publications

The role of allyl ammonium salts in palladium-catalyzed cascade reactions towards the synthesis of spiro-fused heterocycles

The role of allyl ammonium salts in palladium-catalyzed cascade reactions towards the synthesis of spiro-fused heterocycles

Reactivity of Alkynes with M-C Bonds generated through C-H Activation

Tandem Reactions of Ynones: via Conjugate Addition of Nitrogen‐, Carbon‐, Oxygen‐, Boron‐, Silicon‐, Phosphorus‐, and Sulfur‐Containing Nucleophiles

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