- Reductive Elimination to Form C(sp3)-N Bonds from Palladium(II) Primary Alkyl Complexes
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Reductive eliminations to form alkyl-nitrogen bonds are rare, and examples of this reaction from isolated complexes containing simple, unstabilized primary alkyl groups have not been observed. We report the synthesis of stable neopentylpalladium(II) anilido and methyleneamido complexes that undergo reductive elimination to form the C(sp3)-N bonds in N-neopentyl anilines and N-neopentyl imines, respectively. The synthesis and isolation of these complexes were enabled by weak chelation of palladium by P,O ancillary ligands. DFT calculations suggest that neopentylpalladium(II) complexes undergo reductive elimination by a concerted mechanism resembling a migration of the alkyl ligand to the nitrogen either following initial dissociation of the oxygen donor or in concert with lengthening of the Pd-O bond, depending on the identities of the reacting and ancillary ligands.
- Peacock, D. Matthew,Jiang, Quan,Cundari, Thomas R.,Hartwig, John F.
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supporting information
p. 3243 - 3247
(2018/10/05)
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- Efficient transamination under mild conditions: Preparation of primary amine derivatives from carbonyl compounds via imine isomerization with catalytic amounts of potassium tert-butoxide
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1,3-Prototropic rearrangement of N-diphenylmethanimines was successfully performed with a catalytic amount of potassium tert-butoxide. This procedure can also be used with aliphatic and aromatic aldimines and was extended to the isomerization of (1R)-camphorquinone monoimine and N-(4-methoxyphenyl)-4-phenyl-3-iminoazetidin-2-one. The isomerized imines were easily hydrolyzed and isolated as Cbz derivatives.
- Cainelli, Gianfranco,Giacomini, Daria,Trerè, Alessandra,Boyl, Pietro Pilo
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p. 5134 - 5139
(2007/10/03)
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- Radical Cations from N-Alkyl Substituted Imines: an EPR Study
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Following γ-radiolysis of dilute solutions of imines in trichlorofluoromethane at 77 K, EPR spectra of the corresponding radical cations were recorded.For PhCH=NEt amnd PhCH=NCHMe2 the primary 2A' cations were formed, but in each case as a mixt
- Rhodes, Christopher J.,Agirbas, Hikmet
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p. 397 - 402
(2007/10/02)
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