- Molybdenum-catalysed Allylic Amination
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Dioxomolybdenum(VI) complexes including MoO2(dipic)(HMPA) 2a and MoO2(dedtc)2 2b (dipic = 2,6-pyridinedicarboxylate; HMPA = hexamethylphosphoramide; dedtc = N,N-diethyl dithiocarbamate) catalyse the allylic amination of alkenes by phenyl hydroxylamine; the reactions are characterized by a high degree of regioselectivity resulting from double bond migration.
- Srivastava, Anurag,Ma, You-an,Pankayatselvan, Ratnadevi,Dinges, Warren,Nicholas, Kenneth M.
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- On the mechanism of allylic amination catalyzed by iron salts
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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 i
- Srivastava, Radhey S.,Nicholas, Kenneth M.
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- Mechanistic Aspects of Molybdenum-Promoted Allylic Amination
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The mechanism of molybdenum-mediated allylic amination by phenylhydroxylamine has been probed through a variety of kinetics, trapping, and stoichiometric model reaction studies.Specifically, the amination of 2-methyl-2-hexene by (dipic)(HMPA)Mo(η2/s
- Srivastava, Radhey S.,Nicholas, Kenneth M.
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- Mechanistic studies of copper(I)-catalyzed allylic amination
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The reactions of nitrosobenzene and N,N′-diethyl-4-nitrosoaniline with [Cu(CH3CN)4]PF6 provide novel Cu(I) complexes, [Cu(PhNO)3]PF6 (1) and [Cu(Et 2NPhNO)3]PF6 (2); in 2 the copper atom is N-coordinated to the nitrosoarenes in a distorted trigonal planar geometry. Complex 1 is strongly implicated as a reactive intermediate in the Cu(I)-catalyzed allylic amination of olefins based on (i) its isolation from the catalytic reaction, (ii) its stoichiometric regioselective allylic amination of α-methyl styrene (AMS), (iii) the non-involvement of free PhNO in its amination of AMS, and (iv) its function as a catalyst for the amination of alkenes from phenylhydroxylamine. The reaction between AMS and 1 (80°C, dioxane) is first order in both alkene and 1. Relative rate studies of the reaction of 1 with para substituted AMS derivatives gives a Hammett ρ value of -0.035. Alkene adducts isolated from the reaction of 1 with styrene and α-methylstyrene are formulated as [(PhNO)3Cu(η2- alkene)]PF6 (7,8) on the basis of spectroscopic characterization and thermolysis. PM3 and DFT MO calculations support the role of [(alkene)Cu(RNO)3]+ and (η1- or η3-allyl)Cu(RNO)2(RNHOH)+ complexes as probable catalytic intermediates and address the origin of the distinctive reaction regioselectivity. A mechanistic scheme is proposed which is consistent with the accumulated experimental and computational results.
- Srivastava, Radhey S.,Tarver, Nathan R.,Nicholas, Kenneth M.
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p. 15250 - 15258
(2008/09/18)
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- Regioselective Allylic Amination Catalyzed by Iron Salts
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Alkenes react with phenylhydroxylamine in the presence of Fe(II) and Fe(III) salts to produce N-phenyl-N-allyl amines in moderate to good yields.Unsymmetrical substrates react with high regioselectivity giving the products of double bond transition.
- Sristava, Radhey S.,Nicholas, Kenneth M.
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p. 8739 - 8742
(2007/10/02)
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