Rhodium-catalyzed, P-directed selective C7 arylation of indoles

Qiu, Xiaodong; Deng, Hong; Zhao, Yue; Shi, Zhuangzhi

doi:10.1126/sciadv.aau6468

Cited by 80 publications

(23 citation statements)

References 71 publications

(73 reference statements)

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“…Intriguingly, the desired C7‐alkynylated indole 9 a was obtained in 65 % yield after the basic treatment of the crude reaction mixture, and no competing reaction on the pyrrole ring was observed. Other directing groups used in previous reports for the C7‐selective reactions, pivaloyl, phosphine, and phosphine oxide, were ineffective in the present alkynylation protocol.…”

Section: Methodsmentioning

confidence: 89%

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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Section: Methodsmentioning

confidence: 89%

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

2019

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“…Taking advantage of the insights gained in substrate‐directed C−H borylation reactions, our group extended the available directing groups to phosphines. Our initial efforts in phosphine‐directed C−H borylation were reported in 2014, providing the first example of a general phosphine‐directed C−H functionalization and providing access to phosphine boronate esters from valuable phosphine precursors . The key to obtain the desired reactivity in these studies was running the reaction without added ligand.…”

Section: Methodsmentioning

confidence: 99%

Accessing Ambiphilic Phosphine Boronates through C−H Borylation by an Unforeseen Cationic Iridium Complex

et al. 2019

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Ambiphilic molecules,w hich contain aL ewis base and Lewis acid, are of great interest based on their unique ability to activate small molecules.P hosphine boronates are one class of these substrates that have interesting catalytic activity.Direct access to these phosphine boronates is described through the iridium-catalyzed C À Hb orylation of phosphines. An unconventional cationic iridium catalyst was identified as optimal for ar ange of phosphines,p roviding good yields and selectivity across ad iverse class of phosphine boronates (isolated as the borane-protected phosphine). Ac omplimentary catalyst system (quinoline-based silane ligand with [(COD)IrOMe] 2 )was optimal for biphenyl-based phosphines. Selective polyborylation was also shown providing bis-and tris-borylated phosphines.D eprotection of the phosphine boronate provided free ambiphilic phosphine boronates, which do not have detectable interactions between the phosphorus and boron atoms in solution or the solid state.

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“…The authors also demonstrated the C-5 arylation of indoles using different reaction protocols under the copper catalysis (Scheme 8). [25] The arylation of indoles is also well documented by the use of 4d metal catalysts like palladium, [26] rhodium, [27] ruthenium [28] Thearylation by these metals showed the excellent regiocontrol at mild reaction conditions compared to the 3d transition metals. Though the catalysts loading is almost similar, the employment of mild conditions is beneficial with the 4d metal catalysts.…”

Section: Cu-catalyzed Reactionsmentioning

confidence: 99%

C−H Functionalization of Indoles by 3d Transition‐Metal Catalysis

Jagtap

Punji

2019

Asian J Org Chem

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Over the past decade, the use of 3d transition metal for the regioselective C−H bond functionalization of indoles has significantly increased. Particularly, advances in manganese, iron, cobalt, nickel and copper catalysis have demonstrated the selective C(2)−H and C(3)−H arylation, alkenylation, alkynylation and alkylation to a greater extent. Similarly, the C−O and C−N bond‐forming reactions are manifested via direct C−H bond activation by these earth‐abundant metals. The emergence of 3d metals in selective functionalization of the biologically relevant indoles and related heteroarenes would make this protocol more attractive for practical applications. Herein, we provide a brief overview of 3d transition metal‐catalyzed (mostly Mn, Fe, Co, Ni and Cu) C−H functionalization of indoles and related heteroarenes.

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Rhodium-catalyzed, P-directed selective C7 arylation of indoles

Abstract: We report a regioselective direct arylation of indoles at the C7 position with (hetero)aryl bromides.

Cited by 80 publications

References 71 publications

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

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

Accessing Ambiphilic Phosphine Boronates through C−H Borylation by an Unforeseen Cationic Iridium Complex

C−H Functionalization of Indoles by 3d Transition‐Metal Catalysis

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