Intramolecular Carbocupration of <i>N</i>-Aryl-ynamides: A Modular Indole Synthesis

Gati, Wafa; Couty, François; Boubaker, Taoufik; Rammah, Mohamed M.; Evano, Gwilherm

doi:10.1021/ol4013298

Cited by 54 publications

(12 citation statements)

References 55 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Evano 25 reported a modular synthesis of polysubstituted indoles 105 from N -aryl-ynamides 104 . A bromine/lithium exchange of N -(2-bromoaryl)ynamides 104 , followed by a 5- endo - dig carbocupration afforded the substituted indoles efficiently (Scheme 19).…”

Section: Transition Metal Mediated Cyclizationsmentioning

confidence: 99%

Ynamides in Ring Forming Transformations

et al. 2013

View full text Add to dashboard Cite

Conspectus The ynamide functional group activates carbon-carbon triple bonds through an attached nitrogen atom that bears an electron-withdrawing group. As a result, the alkyne has both electrophilic and nucleophilic properties. Through the selection of the electron-withdrawing group attached to nitrogen chemists can modulate the electronic properties and reactivity of ynamides, making these groups versatile synthetic building blocks. The reactions of ynamides also lead directly to nitrogen-containing products, which provides access to important structural motifs found in natural products and molecules of medicinal interest. Therefore, researchers have invested increasing time and research in the chemistry of ynamides in recent years. This Account surveys and assesses new organic transformations involving ynamides developed in our laboratory and in others around the world. We showcase the synthetic power of ynamides for rapid assembly of complex molecular structures. Among the recent reports of ynamide transformations, ring-forming reactions provide a powerful tool for generating molecular complexity quickly. In addition to their synthetic utility, such reactions are mechanistically interesting. Therefore, we focus primarily on the cyclization chemistry of ynamides. This Account highlights ynamide reactions that are useful in the rapid synthesis of cyclic and polycyclic structural manifolds. We discuss the mechanisms active in the ring formations and describe representative examples that demonstrate the scope of these reactions and provide mechanistic insights. In this discussion we feature examples of ynamide reactions involving radical cyclizations, ring-closing metathesis, transition metal and non-transition metal mediated cyclizations, cycloaddition reactions, and rearrangements. The transformations presented rapidly introduce structural complexity and include nitrogen within, or in close proximity to, a newly formed ring (or rings). Thus, ynamides have emerged as powerful synthons for nitrogen-containing heterocycles and nitrogen-substituted rings, and we hope this Account will promote continued interest in the chemistry of ynamides.

show abstract

Section: Transition Metal Mediated Cyclizationsmentioning

confidence: 99%

Ynamides in Ring Forming Transformations

et al. 2013

View full text Add to dashboard Cite

show abstract

“…Moving to the next column of the periodic table, we tried to extend the scope of this carbolithiation to various ynamides. Much more stable than ynamines, ynamides have been shown to undergo carbo‐cuprations11a,c–e and ‐lithiation 11b. The substrates were prepared by following a convenient procedure developed by Hsung, based on a Cu I ‐ or Cu II ‐catalyzed coupling between a secondary “amide” and bromoalkyne 5 , which was itself obtained by bromination of the silver acetylide by N ‐bromosuccinimide (NBS) 3d.…”

Section: Resultsmentioning

confidence: 99%

Intramolecular Carbolithiation of Heterosubstituted Alkynes: An Experimental and Theoretical Study

Lhermet

Ahmad

Hauduc

et al. 2015

Chemistry A European J

View full text Add to dashboard Cite

show abstract

“…Based on our long-standing interest in the chemistry of ynamides, 27 stable nitrogen-substituted alkynes, 28 and in the unique reactivity of activated keteniminium ions 29 derived from these reagents, we envisioned that these building blocks -that are either commercially available or readily prepared by a range of methods 30 -and intermediates might provide a…”

Section: Introductionmentioning

confidence: 99%