Thioether-Directed Selective C4 C–H Alkenylation of Indoles under Rhodium Catalysis

Kona, Chandrababu Naidu; Nishii, Yuji; Miura, Masahiro

doi:10.1021/acs.orglett.8b02038

Cited by 62 publications

(22 citation statements)

References 43 publications

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“… 10 Recently, Miura et al reported the use of thiomethyl ether as an efficient directing group for C4 C–H functionalization. 11 In another study, You described a pivaloyl group-assisted C2/C4 heteroarylation of indoles by a controlled metalation tuning. 12 However, in all the above cases stoichiometric quantities of reagents are required to remove the directing group, which significantly limits the utility of these approaches in a synthesis.…”

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confidence: 99%

Tandem Iridium-Catalyzed Decarbonylative C–H Activation of Indole: Sacrificial Electron-Rich Ketone-Assisted Bis-arylsulfenylation

2021

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Described herein is a decarbonylative tandem C–H bis-arylsulfenylation of indole at the C2 and C4 C–H bonds through the use of pentamethylcyclopentadienyl iridium dichloride dimer ([Cp*IrCl 2 ] 2 ) catalyst and disulfides. A new sacrificial electron-rich adamantoyl-directing group facilitates indole C–H bis-functionalization with a traceless in situ removal. Various differently substituted disulfides can be easily accommodated in this reaction by a coordination to Ir(III) through the formation of six- and five-membered iridacycles at the C2 and C4 positions, respectively. Mechanistic studies show that a C–H activation-induced C–C activation is involved in the catalytic cycle.

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confidence: 99%

Tandem Iridium-Catalyzed Decarbonylative C–H Activation of Indole: Sacrificial Electron-Rich Ketone-Assisted Bis-arylsulfenylation

2021

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“…As a recent contribution in this field, we reported a rhodium‐catalyzed C4‐selective alkenylation using a thioether as a traceless directing group . Encouraged by this achievement, we turned our interest in developing a new catalytic system for the C4‐selective direct alkynylation, and found that the target reaction was feasible using an analogous iridium catalyst and the EBX reagent 2 (Scheme c).…”

Section: Methodsmentioning

confidence: 99%

Iridium‐Catalyzed Direct C4‐ and C7‐Selective Alkynylation of Indoles Using Sulfur‐Directing Groups

2019

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Indoles and their analogues have been one of the most ubiquitous heterocycles during the past century, and extensive studies have been conducted to establish practical synthetic methods for their derivatives. In particular, selective functionalization of the poorly reactive benzenoid core over the pyrrole ring has been a great challenge. Reported herein is an iridium‐catalyzed direct alkynylation of the indole C4‐ and C7‐positions with the assistance of sulfur directing groups. This transformation shows a wide range of functional‐group tolerance with exceptional site selectivity. The directing group can be either easily removed or transformed after catalysis. The synthetic utility of the alkyne fragment is demonstrated by the derivatization into the core structure of natural indole alkaloids.

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“…A thioether‐directed C4‐selective Rh(III)‐catalyzed oxidative alkenylation is developed (Scheme 15). [18] The reaction occurs through a five‐membered rhodacycle. A wide range of alkenes, acrylate esters, acrylonitrile, vinyl phosphonate and styrenes, and electronically varied indoles are tolerated.…”

Section: Functionalization Of C(4)−h Bondmentioning

confidence: 99%

Recent Advances in Metal‐catalyzed Alkylation, Alkenylation and Alkynylation of Indole/indoline Benzenoid Nucleus

Pradhan

Shah

et al. 2020

Chemistry An Asian Journal

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Selective editing of the benzenoid CÀ H bonds (C4À C7) in indoles/indolines has received great interest because functionalized indoles/indolines are featured in many marketed drugs and natural products. Transition-metalcatalyzed directed CÀ H functionalization has thus been developed to manipulate the benzenoid core through CÀ C and C-heteroatom bond formation. This review covers the recent advances in selective CÀ C bond forming reactions, alkylation, alkenylation and alkynylation, over the benzenoid ring (C4À C7) of indoles/indolines using metal catalysis.

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Thioether-Directed Selective C4 C–H Alkenylation of Indoles under Rhodium Catalysis

Cited by 62 publications

References 43 publications

Tandem Iridium-Catalyzed Decarbonylative C–H Activation of Indole: Sacrificial Electron-Rich Ketone-Assisted Bis-arylsulfenylation

Tandem Iridium-Catalyzed Decarbonylative C–H Activation of Indole: Sacrificial Electron-Rich Ketone-Assisted Bis-arylsulfenylation

Iridium‐Catalyzed Direct C4‐ and C7‐Selective Alkynylation of Indoles Using Sulfur‐Directing Groups

Recent Advances in Metal‐catalyzed Alkylation, Alkenylation and Alkynylation of Indole/indoline Benzenoid Nucleus

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