Group 6 metallooxaziridines: preparation, characterization, and reaction with cyclohexanone

Muccigrosso, D. A.; Jacobson, Stephen E.; Apgar, P. A.; Mareš, F.

doi:10.1021/ja00490a048

Cited by 45 publications

(11 citation statements)

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“…In 1978 Sharpless et al and Muccigrosso et al synthesized the molybdenaoxaziridine 157 from a molybdenum dioxo complex 155 and phenyl hydroxylamine 156 (eq 26). 151,152 In relation to the discussion of the chemistry of 157 it should be mentioned that molybdenum peroxides, such as 158, are known to transfer a peroxide oxygen atom to alkenes leading to epoxides. 153 On the basis of earlier success with developing new N-transfer reagents by permutations of oxygen with nitrogen in a variety of oxidants such as SeO 2 and OsO 4 , Sharpless et al hoped that 157, which was characterized by X-ray diffraction and IR spectros- The allylic amination reaction (eq 27) was later developed into a catalytic reaction by Nicholas et al, 154 using a catalytic amount of the molybdenum dioxo complex 155 (10 mol %) and phenyl hydroxylamine 156 as the nitrogen fragment donor.…”

Section: Allylic Amination With Ar−nx and A Metal Catalystmentioning

confidence: 99%

“…In 1978 Sharpless et al and Muccigrosso et al synthesized the molybdenaoxaziridine 157 from a molybdenum dioxo complex 155 and phenyl hydroxylamine 156 (eq 26). , In relation to the discussion of the chemistry of 157 it should be mentioned that molybdenum peroxides, such as 158 , are known to transfer a peroxide oxygen atom to alkenes leading to epoxides …”

Section: 3 Allylic Amination With Ar−nx and A Metal Catalystmentioning

confidence: 99%

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Allylic Amination

1998

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Section: Allylic Amination With Ar−nx and A Metal Catalystmentioning

confidence: 99%

Section: 3 Allylic Amination With Ar−nx and A Metal Catalystmentioning

confidence: 99%

Allylic Amination

1998

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“…Complex I has a quaternary 13 C resonance at d 135.9: this is much lower (10^14 ppm, 8 The 15 N spectrum of complex III has some similar features to that of complex II with the presence of amino groups, b xÀgyÀ and b g xÀ suggested by the ¢rst four signals and complex IV also has a signal indicative of an amino group. The well known 2Y17 insertion reactions of carbon monoxide with p-coordinated nitroso compounds leading to b xÀgyÀ and RNCO formation may be responsible for some of our reaction products.…”

mentioning

confidence: 92%

Solid State Spectroscopic Studies of Molybdenum Oxo Species with Coordinated ONR Groups

Gowenlock¹,

Vasapollo²,

Mele³

et al. 1999

J. Chem. Res.

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“…To date, however, examples of N-transfer from such species to hydrocarbons are rare . In early work Sharpless and Mares reported examples of stoichiometric α-amination of alkenes and cyclohexanone by C-nitroso complexes (molybdooxaziridines), L n MoO(η 2 -RNO). More recently, on the basis of these early communications, we developed molybdenum(VI)- catalyzed allylic aminations using arylhydroxylamines as aminating agents (Scheme ) .…”

Section: Introductionmentioning

confidence: 99%

On the Mechanism of Allylic Amination Catalyzed by Iron Salts

Srivastava

Nicholas

1997

J. Am. Chem. Soc.

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Iron salts catalyze the allylic amination of alkenes by arylhydroxylamines in moderate to good yields and with high regioselectivity resulting from double-bond transposition. The iron-catalyzed reaction of phenylhydroxylamine with representative alkenes in the presence of 2,3-dimethylbutadiene, an effective PhNO trap, produces allyl amines exclusively, excluding the intermediacy of free PhNO in the amination reaction. The reaction of FeCl2,3 with PhNO or PhNHOH produces a novel azo dioxide iron complex, {Fe[Ph(O)NN(O)Ph]3}[FeCl4]2 (1a), whose structure has been established by X-ray diffraction. The structure of 1a features essentially tetrahedral Fe(III)Cl4 - anions and a novel six-coordinate dication having iron(II) bound through the oxygens of three azobenzene N,N-dioxide ligands. Evidence that 1a is the active aminating agent in the catalytic reactions includes (1) its isolation from the catalytic reaction; (2) its facile reaction with alkenes to produce allyl amine in high yield and regioselectivity; (3) its amination of alkenes without the intervention of free PhNO; and (4) its efficient catalysis of amination by PhNHOH. The reaction of 2-methyl-2-pentene (2-MP) with 1a (dioxane, 70 °C) was examined kinetically; the appearance of allylamine was found to be first order in 1a and first order in alkene. Rate constants determined for the reactions of 1a with a set of para-substituted α-methylstyrenes lead to a Hammett ρ value of −3.0. A small kinetic D-isotope effect, 1.4 ± 0.2, is found for the intermolecular amination of α-(trideuteriomethyl)styrene by 1a. Low-temperature reactions of 1a with 2-MP, β-methylstyrene, and styrene produce isolable alkene adducts 3a−c. Thermolysis of 3a in dioxane gives the corresponding allyl amine while treatment of 3a−c with nitrosoarenes regenerates the respective alkenes. IR, NMR, and UV−vis spectroscopic data also support the formulation of 3a−c as alkene complexes. Evidence that azo dioxide complex 1 transfers a PhNO (rather than PhN) unit to alkene, producing an intermediate allylhydroxylamine which is subsequently reduced to the ultimate allyl amine, is provided from model reaction studies and GC/MS monitoring. Various mechanistic pathways are presented and analyzed. The mechanism most consistent with all of the accumulated evidence involves alkene coordination to 1 via dechelation of an azo dioxide ligand, intramolecular RNO transfer to coordinated alkene to produce the allylhydroxylamine, reductive deoxygenation of the allylhydroxylamine to allylamine, and regeneration of azo dioxide complex 1 by oxidation of another PhNHOH molecule by iron(III).

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Group 6 metallooxaziridines: preparation, characterization, and reaction with cyclohexanone

Cited by 45 publications

References 0 publications

Allylic Amination

Allylic Amination

Solid State Spectroscopic Studies of Molybdenum Oxo Species with Coordinated ONR Groups

On the Mechanism of Allylic Amination Catalyzed by Iron Salts

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