Synthesis and Reactivity of Model Intermediates Proposed for the Pd-Catalyzed Remote C–H Functionalization of N‑(2-Haloaryl)acrylamides

We have studied the possible reaction pathways operating in the Pd-catalyzed remote C–H functionalization of N-(2-haloaryl)­acrylamides from an organometallic approach. We have isolated and characterized several proposed reaction intermediates, such as σ-alkyl-Pd complexes and spiro C,C-palladacycle...

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Bibliographic Details
Published inOrganometallics Vol. 36; no. 22; pp. 4465 - 4476
Main Authors Pérez-Gómez, Marta, Navarro, Leticia, Saura-Llamas, Isabel, Bautista, Delia, Lautens, Mark, García-López, José-Antonio
Format Journal Article
LanguageEnglish
Published WASHINGTON American Chemical Society 27.11.2017
Amer Chemical Soc
Subjects
Chemistry
Chemistry, Inorganic & Nuclear
Chemistry, Organic
Physical Sciences
Science & Technology
DIRECTING GROUP
SEQUENTIAL INSERTION
CARBONYLATIVE SPIROLACTONIZATION
PALLADIUM COMPLEXES
MIGRATORY INSERTION
INSERTION REACTIONS
BOND ACTIVATION
REDUCTIVE ELIMINATION
CARBOPALLADATED-BENZYNE
ALKYL COMPLEXES
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Summary:We have studied the possible reaction pathways operating in the Pd-catalyzed remote C–H functionalization of N-(2-haloaryl)­acrylamides from an organometallic approach. We have isolated and characterized several proposed reaction intermediates, such as σ-alkyl-Pd complexes and spiro C,C-palladacycles, and evaluated the role of the base and the auxiliary ligands coordinated to Pd in the remote C–H activation process. In addition, the reactivity of these intermediates toward different unsaturated species such as benzyne, alkynes, and isocyanides has been studied in order to gain further insight into the reaction mechanism leading to functionalized spiro-oxoindoles.
ISSN:0276-7333
1520-6041
DOI:10.1021/acs.organomet.7b00702