Related Experiment Video
Updated: Jun 14, 2026

Facile Preparation of (2Z,4E)-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate
Published on: June 21, 2017
Synthesis and exchange reactions of Ni-dimine-COD, acetylene and olefin complexes
Michael J Sgro1, Douglas W Stephan
1Department of Chemistry, University of Toronto, 80 St. George St. Toronto, Ontario, Canada M5S 3H6.
Abstract:
The complexes MesDADNi(COD) (1), DippDADNi(COD) (2), DippDABNiCOD (3) and DippBIANNi(COD) (5) were readily prepared from Ni(COD)(2). The analogous reaction of the ligand MesBIAN afforded (MesBIAN)(2)Ni (4). The related Ni alkyne complexes DADNi(PhC[triple bond]CPh) (6), DippDABNi(PhC[triple bond]CPh) (7) and DippBIANNi(PhC[triple bond]CPh) (8) are readily prepared by addition of alkyne to solutions of the COD species. The analogous reactions employing tBuDAD ligand with either Ni(COD)(2) alone or Ni(COD)(2) and PhC[triple bond]CPh led only to the known bis-ligand Ni complex, although tBuDADNi(MeCO(2)C[triple bond]CCO(2)Me) (9) is readily prepared. In a similar fashion, the species DippDADNi(MeCO(2)C[triple bond]CCO(2)Me) (10), DippDABNi(Me(3)SiC[triple bond]CSiMe(3)) (11), DippDABNi(MeCO(2)C[triple bond]CCO(2)Me) (12) and DippBIANNi(MeCO(2)C[triple bond]CCO(2)Me) (13) were prepared. Reactions with olefins afforded DippDABNi(MeCO(2)CH=CHCO(2)Me) (14), DippDABNi(MeCO(2)CH=CHPh) (15). Employing isolated (3) or (15) in exchange reactions afforded (7), (11) (14) and (15). Similarly (6) served as a precursor to (10) while (11) reacts with PhC[triple bond]CPh to give (7). The solid state structures of (1), (3)-(7), (9), (11) and (15) are reported.
More Related Videos
Related Concept Videos
Catalysis
[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction
1° Amines to Diazonium or Aryldiazonium Salts: Diazotization with NaNO2 Mechanism
Preparation of Alkynes: Alkylation Reaction
Alkylation of terminal alkynes with primary alkyl halides in the presence of a strong base like sodium amide is one of the common methods for the synthesis of longer carbon-chain alkynes. For example, treatment of 1-propyne with sodium amide followed by reaction with ethyl bromide yields 2-pentyne.
Carboxylic Acids to Methylesters: Alkylation using Diazomethane
Preparation of Amides
The DCC-promoted synthesis of amides begins with the protonation of DCC by carboxylic acid. The protonation makes it a better acceptor. Next, the addition of carboxylate to the protonated carbodiimide gives a reactive acylating agent.
Subsequently, the amine acts as a nucleophile that attacks the acylating agent to form a tetrahedral intermediate. In the...

