Ru-catalysed C–H silylation of unprotected gramines, tryptamines and their congeners

Devaraj, Karthik; Sollert, Carina; Juds, C.; Gates, Paul J.; Pilarski, Lukasz T.

doi:10.1039/c6cc00803h

Cited by 50 publications

(24 citation statements)

References 70 publications

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“…In 2016, Pilarski and co‐workers reported the ruthenium catalysed silylation of aminomethyl benzofuran and benzothiophene derivatives with alkylarylsilanes [45] . Using ruthenium catalyst RuH 2 (CO)(PPh 3 ) 3 with norbornene (nbe) acting as a hydrogen scavenger in toluene at 135 °C for 20 h, benzothiophene derivative 255 was obtained in 75 % yield (Scheme 60).…”

Section: Other Functionalisation (Borylation Phosporylation Carbamomentioning

confidence: 99%

Recent Developments in C−H Functionalisation of Benzofurans and Benzothiophenes

2020

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Benzofurans and benzothiophenes are important pharmaceutical motifs, appearing in a broad range of small molecule therapeutic classes. Often overlooked by synthetic methodologists in favour reactions of the analogous indole bicyclic system, there is nevertheless a plurality of approaches to effecting benzofuran and benzothiophene C−H functionalisations. In this review, we summarise progress in this area over the past five years, including 1) alkylations, 2) arylations and heteroarylations, 3) carboxylations, carbamoylations, and C‐heteroatom bond formations and 4) cyclisations.

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Section: Other Functionalisation (Borylation Phosporylation Carbamomentioning

confidence: 99%

Recent Developments in C−H Functionalisation of Benzofurans and Benzothiophenes

2020

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“…In 2016, Pilarski and co-workers reported the ruthenium-catalysed C2–H silylation of gramines. 47 The reaction used electron-rich ruthenium catalysts to avoid cleavage of the directing group; electrophilic metals are known to cleave the exocyclic amine 48 ( cf. Scheme 3A ).…”

Section: Transition Metal-catalysed C–h Functionalisationmentioning

confidence: 99%

“…The C2–H selective silylation of tryptamines was also efficient, but they did not undergo the analogous C4–H/D exchange. 47 …”

Section: Transition Metal-catalysed C–h Functionalisationmentioning

confidence: 99%

C4–H indole functionalisation: precedent and prospects

et al. 2018

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“…Attempted Suzuki-Miyaura coupling of 16 with the α-bromo-β-alkylcyclopentenone 17 to give the bis-cyclisation precursor 18 was not successful, with only protodehalogenation of 17 observed in the majority of cases. An alternative strategy focusing on the Hiyama coupling of the 2-silyltryptamines 19 and 20, both obtained by CÀ H silylation [8] of 5-methoxytryptamine (21) followed by N-trifluoracetylation, also failed to deliver any of the desired coupled product 3.…”

Section: Full Papersmentioning

confidence: 99%

Synthetic Studies Toward the Flatworm‐Derived Alkaloid Pseudocerosine

Kim

Sperry

2019

ChemistrySelect

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Pseudocerosine, the pigment responsible for the vivid blue spots along the tunic rim of the marine flatworm Pseudoceros indicus, possesses a molecular framework that is unique among heteroaromatic natural products. Herein we provide an overview of several synthetic approaches to the alkaloid pseudocerosine, focusing in particular on the azafulvene‐embedded azepinoindole and the aminal moiety. Two distinct approaches to the azepinoindole core were successful. The first involved C−H borylation of a tryptamine derivative followed by Suzuki‐Miyaura coupling with an α‐bromoenone and base mediated cyclisation. The second involved the selective formation of a conjugated enamine from a tryptamine and an enone, followed by an acid‐mediated Mannich‐type enamine cyclisation. It has also been demonstrated that the unusual aminal present in pseudocerosine can be installed by the reaction of acetamide with a pyridoindole‐based iminium ion. These studies provide valuable insight into the reactivity and stability of the pseudocerosine core structure and serve as a platform for its total synthesis.

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Ru-catalysed C–H silylation of unprotected gramines, tryptamines and their congeners

Abstract: General rightsThis document is made available in accordance with publisher policies. Please cite only the published version using the reference above. Full terms of use are available:

Cited by 50 publications

References 70 publications

Recent Developments in C−H Functionalisation of Benzofurans and Benzothiophenes

Recent Developments in C−H Functionalisation of Benzofurans and Benzothiophenes

C4–H indole functionalisation: precedent and prospects

Synthetic Studies Toward the Flatworm‐Derived Alkaloid Pseudocerosine

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