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. 2024 Sep 13;26(36):7713-7717.
doi: 10.1021/acs.orglett.4c02853. Epub 2024 Aug 29.

Regiodivergent Gold-Catalyzed Rearrangement-Addition Reactions of Sulfenylated Propargylic Carboxylates with Indoles

Nagnath Y More  1 , Paige A Rist  1 , Aniket Gupta  1 , Paul W Davies  1
Affiliations

Regiodivergent Gold-Catalyzed Rearrangement-Addition Reactions of Sulfenylated Propargylic Carboxylates with Indoles

Nagnath Y More et al. Org Lett. .

Abstract

Sulfenylated propargylic carboxylates were introduced to investigate the influence of sulfur substitution in gold-catalyzed alkyne activation pathways. Regiodivergent gold-catalyzed rearrangement and indole capture reactions proceed under mild conditions to give functionalized indole products bearing sulfenylated (Z)-enol carboxylate motifs. Pathways involving both 1,2- and 1,3-carboxylate migrations are achieved selectively, with indole being added in a 1,4 relationship to the sulfenyl group in each case. High levels of selectivity are influenced by the catalyst system, counterion, and carboxylate group.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Scheme 1
Scheme 1. Reactivity from Propargylic Carboxylates
Scheme 2
Scheme 2. Scope of the 1,2-Carboxylate Migration and Indole Addition Process
General conditions: 1 (1.0 equiv.), 2 (3.5 equiv.), IPr*OMeAuCl (5 mol %), and AgOTs (10 mol %) in CH2Cl2 (0.2 M). Yields refer to isolated products. At a 50% ellipsoid probability. Reaction performed on a 3.0 mmol scale.
Scheme 3
Scheme 3. Selective Synthesis of Indole Products from a 1,3-Carboxylate Migration
General conditions: 1 (1.0 equiv., 0.1 mmol), 2 (3.5 equiv., 0.35 mmol), IPr*OMeAuCl (5 mol %), and NaBArF (10 mol %) in CH2Cl2 (0.2 M). Yields of isolated products. Yields determined by 1H NMR spectroscopy of a product mixture with a known amount of methyl 2,5-dinitrobenzoate. At a 50% ellipsoid probability.
Scheme 4
Scheme 4. Transformation of the Funtionalised Indoles
Scheme 5
Scheme 5. Extending the 1,2-Migration and Arylation Reaction with an Aniline Nucleophile
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