Gold-Catalyzed <i>cis</i>-Hydroarylation of Ynamides with Indoles: Regio- and Stereoselective Synthesis of a Class of 2-Vinylindoles

Pirovano, Valentina; Negrato, Marco; Abbiati, Giorgio; Dell’Acqua, Monica; Rossi, Elisabetta

doi:10.1021/acs.orglett.6b02189

Cited by 37 publications

(24 citation statements)

References 57 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[39] We hypothesize that the reactions proceeded through the formation of cyclopropyl gold carbenoids XI from intermediates X, and that these, after ring opening and protodeauration, gave rise to final products 21. In particular, nucleophilic addition of 1 to gold-activated ynamides 19 afforded 2-(α-amidovinyl)-3methylindoles 21 as single isomers in high yields (Scheme 9).…”

Section: Intermolecular Hydroarylation Of Alkynesmentioning

confidence: 99%

“…In particular, nucleophilic addition of 1 to gold-activated ynamides 19 afforded 2-(α-amidovinyl)-3methylindoles 21 as single isomers in high yields (Scheme 9). [39] We hypothesize that the reactions proceeded through the formation of cyclopropyl gold carbenoids XI from intermediates X, and that these, after ring opening and protodeauration, gave rise to final products 21.…”

Section: Intermolecular Hydroarylation Of Alkynesmentioning

confidence: 99%

See 1 more Smart Citation

Gold‐Catalyzed Functionalization Reactions of Indole

Pirovano

2018

Eur J Org Chem

Self Cite

View full text Add to dashboard Cite

This review summarizes the progress achieved in the last fifteen years by application of homogeneous gold catalysis in the field of indole functionalization. Several electrophilic species obtained through gold‐catalyzed π‐activation have in fact been found to react with the nucleophilic positions of indole, thus allowing its efficient manipulation. In order to furnish a complete and clear overview on the role of the catalyst, the review is organized from the perspective of the gold‐activated substrate that is reacting with the indole. In addition, in view of the ability of gold to catalyze tandem and cascade reactions, a separate section describes tandem/cascade protocols useful for the synthesis of complex polycyclic indole derivatives. Finally, gold catalysis has also been employed for the synthesis of indole‐based natural products. For this reason, a dedicated section collects all the work in which the key step to obtain these complex indoles is represented by a gold‐catalyzed reaction.

show abstract

Section: Intermolecular Hydroarylation Of Alkynesmentioning

confidence: 99%

Section: Intermolecular Hydroarylation Of Alkynesmentioning

confidence: 99%

Gold‐Catalyzed Functionalization Reactions of Indole

Pirovano

2018

Eur J Org Chem

Self Cite

View full text Add to dashboard Cite

show abstract

“…A straightforward protocol for the hydroindolylation of ynamides 231 by C-3-substituted indoles 232 leading to regioand stereoselective synthesis of 2-vinylindoles 233 was shown to be catalyzed by [(JohnPhos)Au]NTf 2 (Scheme 39, top). [223] Because of their inherently polarized nature, ynamides coordinate with Au(I) to generate regiodefined electrophilic species. This electrophile interacts with indole nucleophiles forming a transient cyclopropyl Au-carbenoid 232 a followed by rear- with good regiochemical control.…”

Section: Selective Hydroarylation Of π-Systems By Indolesmentioning

confidence: 99%

Catalytic Gold Chemistry: From Simple Salts to Complexes for Regioselective C−H Bond Functionalization

Praveen

Dupeux

Michelet

2021

Chemistry A European J

View full text Add to dashboard Cite

Gold coordinated to neutral phosphines (R 3 P), Nheterocyclic carbenes (NHCs) or anionic ligands is catalytically active in functionalizing various CÀ H bonds with high selectivity. The sterics/electronic nature of the studied CÀ H bond, oxidation state of gold and stereoelectronic capacity of the coordinated auxiliary ligand are some of the associated selectivity factors in gold-catalyzed CÀ H bond functionalization reactions. Hence, in this review a comprehensive update about the action of different types of gold catalysts, from simple to sophisticated ones, on CÀ H bond reactions and their regiochemical outcome is disclosed. This review also highlights the catalytic applications of Au(I)-and Au(III)species in creating new opportunities for the regio-and siteselective activation of challenging CÀ H bonds. Finally, it also intends to stress the potential applications in selective CÀ H bond activation associated with a variety of heterocycles recently described in the literature.

show abstract

“…Recently,y namides bearing an electronwithdrawing group on the nitrogen atom have been made to react with 3-substituted indoles in the presence of gold catalyst 54 (Scheme 56). [126] The obtained C-2 substituted indolylenamides parallel those prepared under Brønsted acid catalysis using unsubstituted indoles portrayed in Scheme34. The envisagedm echanism entails ap reliminary attack at C-3 of the Au-activated alkyne fol- Stable ketenimines can be used insteado ft heir iminium ion analogues 26 in the Co III -catalyzed reaction with N-(2-pyrimidyl) indoles (Scheme 57).…”

Section: C-2 Hydroindolationsmentioning

confidence: 61%

“…Recently, ynamides bearing an electronwithdrawing group on the nitrogen atom have been made to react with 3‐substituted indoles in the presence of gold catalyst 54 (Scheme ) …”

Section: Hydroindolation Of Alkynes and Allenesmentioning

confidence: 99%

Regioselective Direct C‐Alkenylation of Indoles

Petrini

2017

Chemistry A European J

View full text Add to dashboard Cite

The direct introduction of alkenyl groups into the indole framework avoiding its preliminary functionalization can be carried out using different synthetic strategies. Transition-metal complexes facilitate the C-H activation of indoles or alkenes allowing an efficient Csp - Csp bond formation. The hydroindolation of alkynes catalyzed by the same metal complexes or various acidic promoters can also be pursued for the alkenylation process. Conjugate addition of electron-poor alkenes and direct condensation of carbonyl derivatives with indoles are also of interest for this purpose. The regiochemical control can be exploited using the intrinsic C-3 reactivity of the indole ring. The introduction of a suitable directing group at the nitrogen atom allows the preparation of C-2 alkenylated derivatives by transition metal catalyzed reactions. This review collects the fundamental contributions in this field reported in literature during the last fifteen years.

show abstract

Gold-Catalyzed cis-Hydroarylation of Ynamides with Indoles: Regio- and Stereoselective Synthesis of a Class of 2-Vinylindoles

Abstract: A new gold-catalyzed reaction of ynamides with 3-substituted indoles as nucleophiles is reported. The reaction allows for the synthesis of a new class of 2-vinylindole derivatives in good yields via the intermediacy of a cyclopropyl gold-carbenoid species.

Cited by 37 publications

References 57 publications

Gold‐Catalyzed Functionalization Reactions of Indole

Gold‐Catalyzed Functionalization Reactions of Indole

Catalytic Gold Chemistry: From Simple Salts to Complexes for Regioselective C−H Bond Functionalization

Regioselective Direct C‐Alkenylation of Indoles

Contact Info

Product

Resources

About