Direct Transformation of <i>N</i>,<i>N</i>-Dimethylformamide to −CN: Pd-Catalyzed Cyanation of Heteroarenes via C–H Functionalization

Ding, Shengtao; Jiao, Ning

doi:10.1021/ja204063z

Cited by 297 publications

(99 citation statements)

References 63 publications

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“…Dialkyl alkynes exhibited slightly lower reactivity than diaryl alkynes ( O-3n), which showed that the oxygen of the carbonyl group in the product originated from the initial material ( Fig. 3a) [35][36][37] . Further investigation demonstrated that 18 O could also be incorporated into benzo-fused oxindole 3n when extra 18 O-labelled water was added into the reaction system, which suggested that water might be produced and then participate in an apparent oxygen transposition in the cascade reaction (Fig.…”

Section: Resultsmentioning

confidence: 98%

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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Section: Resultsmentioning

confidence: 98%

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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“…[44] Isotope-labeling experiments indicated that both the C and N of the cyano group were derived from DMF [Eqs. (10) and (11) in Scheme 26; TBA = tetra-n-butylammonium].…”

Section: Serving As a Precursor In Cyanation Reactionsmentioning

confidence: 99%

N,N‐Dimethylformamide: A Multipurpose Building Block

2012

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Often used as a common solvent for chemical reations and utilized widely in industry as a reagent, N,N-dimethylformamide (DMF) has played an important role in organic synthesis for a long time. Numerous highly useful articles and reviews discussing its utilizations have been published. With a focus on the performance of DMF as a multipurpose precursor for various units in numerous reactions, this Minireview summarizes recent developments in the employment of DMF in the fields of formylation, aminocarbonylation, amination, amidation, and cyanation, as well as its reaction with arynes.

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“…[43] Wie bei Changs Arbeiten [41] Jiao und Ding entwickelten eine bemerkenswerte Umsetzung, bei der DMF direkt in einen CN-Substituenten umgewandelt wird. [44] Isotopenmarkierungen zufolge stammen hierbei sowohl C als auch N der Cyangruppe aus DMF [Gl. (10) und (11) …”

Section: Dmf Als Vorstufe In Cyanierungenunclassified

N,N‐Dimethylformamid: ein vielseitiger Baustein für die Synthese

Ding

Jiao

2012

Angewandte Chemie

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Die organische Synthese profitiert seit langem von N,N‐Dimethylformamid (DMF), das als Lösungsmittel für chemische Reaktionen und industriell auch als Reagens breit eingesetzt wird. Zu diesen Anwendungen sind bereits zahlreiche hilfreiche Artikel und Übersichten erschienen. Dieser Kurzaufsatz fasst die Verwendung von DMF als Allzweckvorstufe zusammen und stellt die neuen Entwicklungen bei Formylierungen, Aminocarbonylierungen, Aminierungen, Amidierungen, Cyanierungen und in der Reaktion mit Arinen vor.

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Direct Transformation of N,N-Dimethylformamide to −CN: Pd-Catalyzed Cyanation of Heteroarenes via C–H Functionalization

Cited by 297 publications

References 63 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

N,N‐Dimethylformamide: A Multipurpose Building Block

N,N‐Dimethylformamid: ein vielseitiger Baustein für die Synthese

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