Silver‐Catalyzed Cross‐Coupling of Propargylic Alcohols with Isocyanides: An Atom‐Economical Synthesis of 2,3‐Allenamides

Liu, Jianquan; Liu, Zhenhua; Wu, Nannan; Liao, Peiqiu; Bi, Xihe

doi:10.1002/chem.201304255

Cited by 67 publications

(16 citation statements)

References 111 publications

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“…1c) 17,30,31 , which were confirmed by single crystal X-ray diffraction analysis ( Supplementary Figs 42 and 43). This tandem reaction was disclosed to involve an apparent oxygen transposition via dehydration-rehydration from the indolyl-3-carbonyl group to the pyrrole C2-position to forge a new carbonyl bond [32][33][34] . Based on mechanism investigation, the reactivity and the scope of reaction were further improved.…”

mentioning

confidence: 99%

Unexpected regioselective carbon–hydrogen bond activation/cyclization of indolyl aldehydes or ketones with alkynes to benzo-fused oxindoles

Liu

Song

et al. 2014

Nat Commun

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Rhodium-catalyzed carbon-hydrogen bond activation has attracted great interest in the construction of carbon-carbon and carbon-heteroatom bonds. In recent years, transition metal-mediated oxygen transposition through a 'dehydration-rehydration' process has been considered as a promising strategy towards oxygen-functionalized compounds. Here we describe an unexpected rhodium-catalyzed regioselective carbon-hydrogen bond activation/ cyclization of easily available indolyl aldehydes or ketones with alkynes to afford benzo-fused oxindoles, involving the sequential carbonyl-assisted carbon-hydrogen activation of the indole ring at the 4-position, [4 þ 2] cyclization, aromatization via dehydration, nucleophilic addition of water to iminium and oxidation. Isotopic labelling experiments disclose the occurrence of apparent oxygen transposition via dehydration-rehydration from the indolyl-3-carbonyl group to the 2-position of pyrrole to forge a new carbonyl bond. The tandem reaction has been used as the key step for the concise synthesis of priolines, a type of alkaloid isolated from the roots of Salvia prionitis.

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confidence: 99%

Unexpected regioselective carbon–hydrogen bond activation/cyclization of indolyl aldehydes or ketones with alkynes to benzo-fused oxindoles

Liu

Song

et al. 2014

Nat Commun

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“…The Ag-catalyzed C-C coupling reaction of isocyanides and propargylic alcohols 205 with accompanying oxygen transposition yields diverse allenamides 206 in moderate to good yields (Scheme 63). 128 A plausible mechanism proceeds by generation of the Ag acetylide 207 followed by isocyanide insertion giving 208; addition of another molecule of propargylic alcohol 205 to 208 along with intramolecular H-migration and rearrangement delivers Ag acetylide 209. M. Shiri et al…”

Section: Scheme 62 Pd-catalyzed Reaction Of Allyl Esters and Isocyanidesmentioning

confidence: 99%

Transition Metal and Inner Transition Metal Catalyzed Amide Derivatives Formation through Isocyanide Chemistry

et al. 2020

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The synthesis of amides is a substantial research area in organic chemistry because of their ubiquitous presence in natural products and bioactive molecules. The use of easily accessible isocyanides as amidoyl (carbamoyl) synthons in cross-coupling reactions using transition metal and inner transition metöal catalysts is a current trend in this area. Isocyanides, owing to their coordination ability as a ligand and inherent electronic properties for reactions with various partners, have expanded the potential application of these transformations for the preparation of novel synthetic molecules and pharmaceutical candidates. This review gives an overview of the achievements in isocyanide-based transition metal and inner transition metal catalyzed amide formation and discusses highlights of the proposed distinct mechanisms.1 Introduction2 Synthesis of Arenecarboxamides3 Synthesis of Alkanamides4 Synthesis of Cyclic Amides5 Formation of Alkynamides6 Formation of Acrylamide-like Molecules7 Formation of Ureas and Carbamates8 Conclusion

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“…In 2014, Bi and co-workers reported an Ag2CO3-catalyzed cross-coupling reaction of propargylic alcohols 8 with isocyanides 9 to give 2,3-allenamides 10 (Scheme 6) [19]. Although the reaction mechanism is not clear, this reaction involves a unique β-C-C coupling and oxygen transposition of propargylic alcohols.…”

Section: Terminal Alkynes: Cross-coupling Reactionsmentioning

confidence: 99%

“…Indolizine is a basic organic building block for many alkaloids and bioactive molecules, so the development of regioselective synthetic pathways is an attractive topic in organic synthesis [21]. This reaction allows the highly selective synthesis of indolizines from readily available starting materials via a 5-endo-dig cyclization between the silver phenylacetylide generated from alkyne 1 and a chelated In 2014, Bi and co-workers reported an Ag 2 CO 3 -catalyzed cross-coupling reaction of propargylic alcohols 8 with isocyanides 9 to give 2,3-allenamides 10 (Scheme 6) [19]. Although the reaction mechanism is not clear, this reaction involves a unique β-C-C coupling and oxygen transposition of propargylic alcohols.…”

Section: Terminal Alkynes: Cross-coupling Reactionsmentioning

confidence: 99%

“…The coordination of Ag(I) generated internal alkyne 6-III, which is cyclized by an intramolecular nucleophilic addition to provide cyclic intermediate 6-IV, and subsequent aromatization and protodemetallation give highly substituted pyrrole 7 as the product. In 2014, Bi and co-workers reported an Ag2CO3-catalyzed cross-coupling reaction of propargylic alcohols 8 with isocyanides 9 to give 2,3-allenamides 10 (Scheme 6) [19]. Although the reaction mechanism is not clear, this reaction involves a unique β-C-C coupling and oxygen transposition of propargylic alcohols.…”

Section: Terminal Alkynes: Cross-coupling Reactionsmentioning

confidence: 99%

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Recent Organic Transformations with Silver Carbonate as a Key External Base and Oxidant

et al. 2019

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Silver carbonate (Ag2CO3), a common transition metal-based inorganic carbonate, is widely utilized in palladium-catalyzed C–H activations as an oxidant in the redox cycle. Silver carbonate can also act as an external base in the reaction medium, especially in organic solvents with acidic protons. Its superior alkynophilicity and basicity make silver carbonate an ideal catalyst for organic reactions with alkynes, carboxylic acids, and related compounds. This review describes recent reports of silver carbonate-catalyzed and silver carbonate-mediated organic transformations, including cyclizations, cross-couplings, and decarboxylations.

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Silver‐Catalyzed Cross‐Coupling of Propargylic Alcohols with Isocyanides: An Atom‐Economical Synthesis of 2,3‐Allenamides

Cited by 67 publications

References 111 publications

Unexpected regioselective carbon–hydrogen bond activation/cyclization of indolyl aldehydes or ketones with alkynes to benzo-fused oxindoles

Unexpected regioselective carbon–hydrogen bond activation/cyclization of indolyl aldehydes or ketones with alkynes to benzo-fused oxindoles

Transition Metal and Inner Transition Metal Catalyzed Amide Derivatives Formation through Isocyanide Chemistry

Recent Organic Transformations with Silver Carbonate as a Key External Base and Oxidant

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