Ketene imines

and, Marvin W. Barker; McHenry, William E.

doi:10.1002/9780470771617.ch4

Cited by 20 publications

(11 citation statements)

References 10 publications

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“…In agreement with this mechanism, no cyclization occurs for the xylyl derivative 7 d , because of the two methyl groups blocking positions 2 and 6 in the phenyl ring. N ‐Aryl ketenimines have been used occasionally in the synthesis of quinolines by either intermolecular11 or intramolecular12 cyclization processes, but, to our knowledge, this is the first time that a cumulene residue has been involved in such a process.…”

Section: Resultsmentioning

confidence: 99%

High Structural Control in Metal‐Mediated Synthesis of New Functionalized Diphosphines Using Diphosphinoketenimines as Precursors

Mosquera

Ruiz

Garcı́a

et al. 2006

Chemistry A European J

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The diphosphinoketenimine ligand in the neutral complexes fac-[MnI(CO)(3){(PPh(2))(2)C=C=NR}] (1 a: R = Ph; 1 b: R = p-tolyl) undergoes nucleophilic attack by MeLi and nBuMgCl yielding, after hydrolysis, the diphosphinoenamine-containing complexes fac-[MnI(CO)(3){(PPh(2))(2)C=C(R')NHR}] (3 a,b: R' = Me; 4 a,b: R' = nBu). Complex 1 a reacts under the same conditions with H(2)C=C=CHMgBr to afford fac-[MnI(CO)(3){(PPh(2))(2)C=C(CH(2)CC[triple chemical bond]CH)NHR}] (5 a), which contains a terminal alkyne group on the alpha-carbon atom of the diphosphinoenamine ligand. The cationic complexes fac-[Mn(CO)(4){(PPh(2))(2)C=C=NR}](+) (6) react with H(2)C=C=CHMgBr to afford diphosphinomethanide derivatives bearing three different types of functional groups, depending upon the substituent on the nitrogen atom of the ketenimine: cumulene in fac-[Mn(CO)(4){(PPh(2))(2)C--C(CH=C=CH(2))=N-xylyl}] (7 d), internal alkyne in fac-[Mn(CO)(4){(PPh(2))(2)C--C(C[triple chemical bond]CCH(3))=NtBu}] (8), and quinoline in 9 (R = Ph), whose formation implies an unusual cyclization process. Protonation of 7 d, 8, and 9 with HBF(4) occurs at the nitrogen atom to give the cationic derivatives 10 d, 11, and 12, respectively, which contain the corresponding functionalized diphosphine ligands. Irradiation of 3 a,b and 4 a,b with Vis/UV light makes it possible to isolate the free ligands (PPh(2))(2)C=C(R')NHR (13 a,b and 14 a,b), completing the metal-assisted synthesis of these novel functionalized diphosphines. Irradiation of 12 with Vis/UV light generates free phosphinoquinoline ligand 15, which readily affords a complex 16 containing 15 as a P,N-chelating ligand when treated with [PdCl(2)(NCMe)(2)], thus demonstrating its coordination capability.

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Section: Resultsmentioning

confidence: 99%

High Structural Control in Metal‐Mediated Synthesis of New Functionalized Diphosphines Using Diphosphinoketenimines as Precursors

Mosquera

Ruiz

Garcı́a

et al. 2006

Chemistry A European J

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“…The N,N-chelate ring of 2 binds formally with one dative and one coordinate covalent V−N interaction forming a five-membered diazametallacyle with an exocyclic keteneimine functionality . A strong absorption in the IR spectrum at 1987 cm -1 may be attributed to the keteneimine, and a medium band at 1518 cm -1 is consistent with a CN double bond. The magnetic moment of 2 was measured as 2.79 μ B , and its 1 H NMR spectrum was featureless.…”

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confidence: 93%

Synthesis and Reactivity of a Vanadium(III)−Methyl Complex Stabilized by Hexamethylsilazanate Ligands

Gerlach

Arnold

1996

Organometallics

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The vanadium(III) − Me complex [(Me 3 Si) 2 N] 2 VMe(THF) ( 1 ) was prepared by reaction of the corresponding V − Cl derivative with Me 2 Mg, and its X-ray crystal structure has been determined. The methyl complex reacts with 3 equiv of RNC (R = Bu t , Xylyl) to give isocyanide-coupled products, is oxidized by styrene oxide affording a V(IV) μ-O dimer, and on heating eliminates CH4 via metalation of a −N(SiMe3)2 ligand.

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“…Ketenimines are an important class of compounds that are recognized as useful synthetic intermediates or synthons in chemistry. Since Staudinger reported the first ketenmines in 1920, much of the knowledge of these analogous compounds has flourished within the last hundred years . Because of their unique properties related to the presence of an ethylene-like C–C double bond and an azomethine-like C–N double bond, ketenimines have opened a wide range of available reaction paths.…”

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confidence: 99%

Palladium-Catalyzed Migratory Insertion of Isocyanides for Synthesis ofC-Phosphonoketenimines

Yang

Cheng

et al. 2016

ACS Catal.

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An efficient method for the synthesis of C-phosphonoketenimines through palladium-catalyzed migratory insertion of isocyanides has been developed for the first time. This procedure tolerates wide functional groups and has a good atom economy. Further transformations of the products, which are useful building blocks for the β-aminophosphonates, β-aminovinylphosphonates, and C-phosphorylated tetrazoles, indicate potential synthetic utility.

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Ketene imines

Cited by 20 publications

References 10 publications

High Structural Control in Metal‐Mediated Synthesis of New Functionalized Diphosphines Using Diphosphinoketenimines as Precursors

High Structural Control in Metal‐Mediated Synthesis of New Functionalized Diphosphines Using Diphosphinoketenimines as Precursors

Synthesis and Reactivity of a Vanadium(III)−Methyl Complex Stabilized by Hexamethylsilazanate Ligands

Palladium-Catalyzed Migratory Insertion of Isocyanides for Synthesis ofC-Phosphonoketenimines

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