Theoretical evaluation of the carbene-based site-selectivity in gold(<scp>iii</scp>)-catalyzed annulations of alkynes with anthranils

Wang, Kaifeng; Wu, Qiao; Bi, Siwei; Liu, Lingjun; Chen, Guang; Li, Yulin; James, Tony D.; Liu, Yuxia

doi:10.1039/d0cc07440c

Cited by 5 publications

(6 citation statements)

References 30 publications

(4 reference statements)

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“…Combining this with our previous study, we give a conclusion that the ligand exchange for two coordinate Au(I) complexes normally undergoes a concerted step rather than a dissociative mechanism . The associative mechanism ( 1 + S2 → S1-AuCl-S2 → 2 + S1 ) is also infeasible due to the fact that Au(I) normally prefers a two coordinate linear structure rather than a three coordinate plane triangular structure …”

Section: Resultssupporting

confidence: 73%

Insights into α-Alkynylation and α-Allenylation of Aldehydes under the Synergisitic Catalysis of Gold/Amine: A DFT Study

Zhang

et al. 2022

J. Org. Chem.

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A mechanistic investigation of α-alkynylation and α-allenylation of aldehydes under the synergistic catalysis of AuCl/amine was performed using density functional theory (DFT) calculations. For such a reaction that delivers two products, this study reveals that the reaction undergoes such a mechanistic mode: reactants → alkynyl product → allenyl product, implying that the allenyl product cannot be obtained directly from reactants. The product ratio obtained experimentally was rationalized based on the computed results that both products can reversibly interconvert with AuCl as the catalyst and with N-containing Lewis bases as additives such as 4,5-diazafluorenone. For the relative stability of alkynyl versus allenyl compounds, unsaturated substituents are found to favor the allenyl compounds.

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Section: Resultssupporting

confidence: 73%

Insights into α-Alkynylation and α-Allenylation of Aldehydes under the Synergisitic Catalysis of Gold/Amine: A DFT Study

Zhang

et al. 2022

J. Org. Chem.

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“…It is worth noting that Au(III) species also catalyze a similar transformation, although the final outcome seems strongly dependent on the counterion chaperoning gold. [6,14,15] 4 | COMPUTATIONAL SECTION Throughout this work, the Kohn-Sham formulation of density functional theory was employed. [16] The metahybrid density functional M06 [17] has been used with the extended double-ζ quality def2-SVPP basis set for all the static calculations.…”

Section: Discussionmentioning

confidence: 99%

“…It is worth noting that Au(III) species also catalyze a similar transformation, although the final outcome seems strongly dependent on the counterion chaperoning gold. [ 6,14,15 ]…”

Section: Discussionmentioning

confidence: 99%

On the mechanism of the Au(I)‐mediated addition of alkynes to anthranils to furnish 7‐acylindoles

Papanastasiou

Litinas

Faza

et al. 2022

J of Physical Organic Chem

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Indole is a very common structural motif in alkaloids with a remarkable history in pharma industry. In the continuous search for more direct and efficient access to these valuable structures, a new and rather elegant approach was found by Jin and coworkers, which involved a gold(I)‐mediated addition of alkynes onto anthralins. This approach selectively furnishes 7‐acylindoles in a rather expeditious way, and it has been shown to be compatible with a large range of decorated reactants, both at the alkyne side and at the anthralin side. We studied the mechanism of this reaction with a set of different alkynes, including disubstituted ones, to establish similarities and differences between them and to aid in the elucidation of key steps in the reaction pathway. The observed regioselectivity seems to be connected to the irreversible formation of a key α‐imino gold carbene intermediate, common to all reaction profiles, through the initial regioselective nucleophilic attack of the anthranil N atom onto the alkyne fragment.

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“…287 For these transformations, a unified rationale for Br-migration on α-amino gold( iii )-carbene is proposed by DFT calculations. 288 A N-donation/abstraction substitution mechanism is established for the substituted anthranils, and direct C–H nucleophilic attack is considered to be involved with the substituted anthranils. The computational studies provide insight for developing new α-amino gold( iii )–carbene-catalyzed reactions.…”

Section: Carbene Insertion To Aryl C(sp2)–h Bondsmentioning

confidence: 99%

Recent advances in transition-metal-catalyzed carbene insertion to C–H bonds

Huang

et al. 2022

Chem. Soc. Rev.

168

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Theoretical evaluation of the carbene-based site-selectivity in gold(iii)-catalyzed annulations of alkynes with anthranils

Abstract: The mechanisms and origins of multiple-site selectivities of versatile gold(iii)-catalyzed annulations of alkynes with anthranils are theoretically unraveled.

Cited by 5 publications

References 30 publications

Insights into α-Alkynylation and α-Allenylation of Aldehydes under the Synergisitic Catalysis of Gold/Amine: A DFT Study

Insights into α-Alkynylation and α-Allenylation of Aldehydes under the Synergisitic Catalysis of Gold/Amine: A DFT Study

On the mechanism of the Au(I)‐mediated addition of alkynes to anthranils to furnish 7‐acylindoles

Recent advances in transition-metal-catalyzed carbene insertion to C–H bonds

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