Catalytic metathesis of simple secondary amides

Angewandte Chemie - International Edition

Volumn 46, Issue 5, 2007, Pages 761-763

  Bell, Christen M ^a   Kissounko, Denis A ^a   Gellman, Samuel H ^a   Stahl, Shannon S ^a  

^a UNIVERSITY OF WISCONSIN MADISON   (United States)

Author keywords

Amides; Dynamic covalent chemistry; Homogeneous catalysis; Metathesis; Synthetic methods

Indexed keywords

CATALYSIS; REACTION KINETICS; SUBSTRATES;

AMIDES; DYNAMIC COVALENT CHEMISTRY; HOMOGENEOUS CATALYSIS; METATHESIS; SYNTHETIC METHODS;

NITROGEN COMPOUNDS;

EID: 33846544889     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200603588     Document Type: Article

References (26)

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17. III-catalyzed transamidation is proportional to the concentrations of the metal and the amine (see Ref. [3b]). Both of these species are present at low concentration in amide metathesis. Thus far, we have not identified practical conditions for amide metathesis which involves a transamidation mechanism.
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19. This strategy finds loose precedent in the anionic, ring-opening polymerization (ROP) of lactams, which employs imide (N-acyllactam) and Brønsted base coinitiators. Polymer chain initiation and propagation are believed to proceed through attack of a deprotonated lactam on the imide carbonyl of the initiator or polymer chain end. For a discussion, see: K. Hashimoto, Prog. Polym. Sci. 2000, 25, 1411-1462.
20. Typical reaction procedure: In a disposable vial (4 mL), a 1:1 mixture of amides (0.23 mmol) and base (20 mol%, 0.046 mmol) were mixed in diglyme (0.8 mL) under nitrogen. To this mixture, imide initiator (20 mol %, 0.046 mmol) and triphenylmethane (0.018 mol, 4.4 mg) as an internal standard were added. The vials were sealed under nitrogen and placed into a 48-well parallel reactor mounted on a vortexing mixer. The reactions were heated to 120°C for 18 h and quenched with water (1 mL). The organics were extracted into diethyl ether, and product ratios were determined by GC analysis relative to the triphenylmethane standard.
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25. For imide preparation, see: R. P. Mariella, K. H. Brown, J. Org. Chem. 1971, 36, 735-737.
26. One reviewer noted that O-acylated intermediates might participate in these reactions. Understanding the role of such intermediates, if they indeed exist, and identifying catalyst-decomposition pathways might reveal ways to achieve improved catalytic activity at lower temperature.