<i>N</i>-Alkynyl Imides (Ynimides): Synthesis and Use as a Variant of Highly Labile Ethynamine

Sueda, Takuya; Oshima, Ayumi; Teno, Naoki

doi:10.1021/ol2014973

Cited by 60 publications

(27 citation statements)

References 32 publications

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“…Sueda 47 applied their ynimides 207 to the copper-mediated Huisgen's azide-[3 + 2] cycloaddition giving 4-phthalimido-1-benzyl-1,2,3-triazole 208 (Scheme 39). …”

Section: Cycloadditions and Formal Cycloadditionsmentioning

confidence: 99%

Ynamides in Ring Forming Transformations

et al. 2013

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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.

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“…Sueda 47 applied their ynimides 207 to the copper-mediated Huisgen's azide-[3 + 2] cycloaddition giving 4-phthalimido-1-benzyl-1,2,3-triazole 208 (Scheme 39). …”

Section: Cycloadditions and Formal Cycloadditionsmentioning

confidence: 99%

Ynamides in Ring Forming Transformations

et al. 2013

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“…In 2011, the first synthesis of alkynyl imides was reported by Sueda and co-workers using alkynyl(triaryl)bismuthonium salts and a copper catalyst (Scheme 30 8). 16 The mechanism proposed starts with a ligand exchange with the imide. The Cu(I) species then undergoes an oxidative addition with the alkynyl(triaryl)bismuthonium and then the product is obtained via reductive elimination.…”

Section: Methodsmentioning

confidence: 99%

Electrophilic alkynylation: the dark side of acetylene chemistry

2012

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In addition to the well-established nucleophilic alkynylation, the use of electrophilic alkynes can expand 5 tremendously the scope of acetylene transfer reactions. The use of metal catalysis has recently led to a rebirth of this research area. Halogenoalkynes, hypervalent alkynyliodoniums, acetylene sulfones and in situ oxidation of terminal acetylenes are the most often used for electrophilic alkynylation. Heteroatoms such as N, O, S and P can be now efficiently alkynylated. For C-C bond formation, electrophilic acetylenes can be coupled with different organometallics reagents. Recently, the first breakthrough in 10 direct C-H and C=C bond alkynylation have also been reported. Finally, sulfonyl acetylenes are efficient for alkyne transfer on carbon-centered radicals.

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“…2-(2-Phenylethynyl)-2,3-dihydro-1H-isoindole-1,3-dione (1e). 26 The reaction was conducted according to the general procedure in the presence of Cu(OAc) 2 (3.9 mmol, 710 mg, 0.2 equiv), phtalimide (97.7 mmol, 14.38 g, 5.0 equiv), Na 2 CO 3 (39.1 mmol, 4.14 g, 2.0 equiv), a solution of pyridine (39.1 mmol, 3.15 mL, 2.0 equiv) in dry toluene (100 mL) and phenylacetylene (19.5 mmol, 2.15 mL, 1.0 equiv) was added in dry toluene (100 mL). Purification by flash chromatography on silica gel (pentane/ethyl acetate (100/0 to 95/5)) led to ynamide 1e (860 mg, 18% yield) as colorless oil.…”

Section: General Procedures For Ynamides Synthesismentioning

confidence: 99%

Iron(II)/copper(I)-mediated stereoselective carbozincation of ynamides. One-pot synthesis of α-allyl-tetrasubstituted-enamides

et al. 2017

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The iron(II) chloride-and copper(I) iodide-mediated carbozincation of a panel of substituted ynamides is described in this article. The reaction is totally regio-and stereoselective. Experiments showed that the reaction mediated with Fe(II) was more substrate dependent than the reaction performed with Cu(I). Interestingly, in the presence of allylbromide, stereoselective carboallylation can be achieved for the first time in a one-pot procedure, leading to skipped dienamides. .

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N-Alkynyl Imides (Ynimides): Synthesis and Use as a Variant of Highly Labile Ethynamine

Cited by 60 publications

References 32 publications

Ynamides in Ring Forming Transformations

Ynamides in Ring Forming Transformations

Electrophilic alkynylation: the dark side of acetylene chemistry

Iron(II)/copper(I)-mediated stereoselective carbozincation of ynamides. One-pot synthesis of α-allyl-tetrasubstituted-enamides

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