Steric, Electronic and Conformational Synergistic Effects in the Gold(I)‐catalyzed α<i>‐</i>C−H Bond Functionalization of Tertiary Amines**

Rayo, David Fabian León; Mansour, Ali; Wu, Wenbin; Bhawal, Benjamin N.; Gagosz, Fabien

doi:10.1002/ange.202212893

Angewandte Chemie

2022

DOI: 10.1002/ange.202212893

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Steric, Electronic and Conformational Synergistic Effects in the Gold(I)‐catalyzed α‐C−H Bond Functionalization of Tertiary Amines**

David Fabian León Rayo

Ali Mansour

Wenbin Wu

et al.

Abstract: Direct CÀ H bond functionalization is a useful strategy for the straightforward formation of CÀ C and CÀ Heteroatom bonds. In the present work, a unique approach for the challenging electrophilic Au-catalyzed α-CÀ H bond functionalization of tertiary amines is presented. Electronic, steric and conformational synergistic effects exerted by the use of a malonate unit in the substrate were key to the success of this transformation. This new reactivity was applied to the synthesis of tetrahydro-γ-carboline product… Show more

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Cited by 5 publications

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Electronic and Steric Effects in a Gold(I)‐Catalyzed Intramolecular C(sp³)−H Bond Activation Reaction of 1‐Bromoalkynes

Miguélez,

Arto,

Semleit

et al. 2024

Adv Synth Catal

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The functional group compatibility of our recently disclosed gold(I)‐catalyzed cycloisomerization of 1‐bromoalkynes is studied in detail. Two main features are addressed, the minimum distances at which polar functional groups are tolerated and the influence of both electronic and steric effects on the performance of aryl ether derivatives. Moreover, robustness assessment experiments have been carried out shedding light on the factors dictating functional group tolerance. In addition, the reaction has been applied to the synthesis of a key intermediate in the total synthesis of a natural product and a heterobifunctional molecule. DFT calculations have shed light on the mechanistic features behind the observed reactivity trends. On one hand, the destabilization of the TS by the proximity of the polar group may hamper the reactivity for proximal functional groups. On the other hand, some polar functional groups are not tolerated regardless of their position due to the preferential coordination of gold to the oxygen atom over the alkyne, resulting presumably in competitive catalyst deactivation pathways.

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Electronic and Steric Effects in a Gold(I)‐Catalyzed Intramolecular C(sp³)−H Bond Activation Reaction of 1‐Bromoalkynes

Miguélez,

Arto,

Semleit

et al. 2024

Adv Synth Catal

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show abstract

Gold(I)‐Catalyzed Benzylic C(sp³)−H Functionalizations: Divergent Synthesis of Indole[a]‐ and [b]‐Fused Polycycles**

et al. 2022

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Phenyl azidessubstituted by an (alkylphenyl)ethynyl group facilitate benzylic sp 3 (CÀ H) functionalization in the presence of a JohnPhosAu catalyst, resulting in indole-fused tetra-and pentacycles via divergent N-or C-cyclization. The chemoselectivity is influenced depending on the counter-anion, the electron density of the α-imino gold(I) carbene, and the alkyl groups stabilizing the benzylic carbocation originating from a 1,5-hydride shift. An isotopic labeling experiment demonstrates the involvement of an indolylgold(I) species resulting from a tautomerization that is much faster than the deauration. The formation of a benzylic sp 3 (CÀ H) functionalization leading to an indole-fused seven-membered ring is also demonstrated.

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Copper‐Catalyzed Enantioselective Doyle–Kirmse Reaction of Azide‐Ynamides via α‐Imino Copper Carbenes

Liu

Chen

et al. 2023

Angewandte Chemie

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2,3]-Sigmatropic rearrangement reaction involving sulfonium ylide (Doyle-Kirmse reaction) generated from metal carbenes represents one of the powerful methods for the construction of C(sp 3 )À S and CÀ C bonds. Although significant advances have been achieved, the asymmetric versions via the generation of sulfonium ylides from metal carbenes have been rarely reported to date, and they have so far been limited to diazo compounds as metal carbene precursors. Here, we describe a copper-catalyzed enantioselective Doyle-Kirmse reaction via azide-ynamide cyclization, leading to the practical and divergent assembly of an array of chiral [1,4]thiazino [3,2-b]indoles bearing a quaternary carbon stereocenter in generally moderate to excellent yields and excellent enantioselectivities. Importantly, this protocol represents a unique catalytic asymmetric Doyle-Kirmse reaction via a non-diazo approach and an unprecedented asymmetric [2,3]-sigmatropic rearrangement via α-imino metal carbenes.

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Steric, Electronic and Conformational Synergistic Effects in the Gold(I)‐catalyzed α‐C−H Bond Functionalization of Tertiary Amines**

Cited by 5 publications

References 77 publications

Electronic and Steric Effects in a Gold(I)‐Catalyzed Intramolecular C(sp³)−H Bond Activation Reaction of 1‐Bromoalkynes

Electronic and Steric Effects in a Gold(I)‐Catalyzed Intramolecular C(sp³)−H Bond Activation Reaction of 1‐Bromoalkynes

Gold(I)‐Catalyzed Benzylic C(sp³)−H Functionalizations: Divergent Synthesis of Indole[a]‐ and [b]‐Fused Polycycles**

Copper‐Catalyzed Enantioselective Doyle–Kirmse Reaction of Azide‐Ynamides via α‐Imino Copper Carbenes

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Steric, Electronic and Conformational Synergistic Effects in the Gold(I)‐catalyzed α‐C−H Bond Functionalization of Tertiary Amines**

Cited by 5 publications

References 77 publications

Electronic and Steric Effects in a Gold(I)‐Catalyzed Intramolecular C(sp3)−H Bond Activation Reaction of 1‐Bromoalkynes

Electronic and Steric Effects in a Gold(I)‐Catalyzed Intramolecular C(sp3)−H Bond Activation Reaction of 1‐Bromoalkynes

Gold(I)‐Catalyzed Benzylic C(sp3)−H Functionalizations: Divergent Synthesis of Indole[a]‐ and [b]‐Fused Polycycles**

Copper‐Catalyzed Enantioselective Doyle–Kirmse Reaction of Azide‐Ynamides via α‐Imino Copper Carbenes

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Product

Resources

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Electronic and Steric Effects in a Gold(I)‐Catalyzed Intramolecular C(sp³)−H Bond Activation Reaction of 1‐Bromoalkynes

Electronic and Steric Effects in a Gold(I)‐Catalyzed Intramolecular C(sp³)−H Bond Activation Reaction of 1‐Bromoalkynes

Gold(I)‐Catalyzed Benzylic C(sp³)−H Functionalizations: Divergent Synthesis of Indole[a]‐ and [b]‐Fused Polycycles**