Rational design in homogeneous catalysis. Ir(I)-catalyzed addition of aniline to norbornylene via N-H activation

David Milstein, Joseph C. Calabrese, David Milstein

Research output: Contribution to journalArticle

325 Citations (Scopus)

Abstract

The first successful demonstration of the amination of an olefin by a transition-metal-catalyzed N-H activation mechanism was accomplished in a stepwise manner with an Ir(I) catalyst and the substrates aniline and norbornylene. The initial N-H oxidative addition step envisioned in such a mechanism was demonstrated for the complexes Ir(PMe3)4PF6, Ir(PMe3)3(C8H14)Cl, and Ir(PEt3)3Cl, all of which gave rise to stable cis anilido hydride complexes when reacted with aniline. The second step olefin insertion, was accomplished from the reaction of Ir(PEt3)2(C2H4)2Cl (1) with aniline and norbornylene. The resulting insertion product, Ir(PEt3)2(NHPhC7H10)(H)Cl (6), was characterized by NMR spectroscopy and single-crystal X-ray diffraction and was found to have an azoiridacyclobutane type structure. The relevant crystal data for 6 are a = 10.702 (3) Å, b = 13.176 (21) Å, c = 19.498 (5) Å, β = 98.61 (2); P21/c, T = -70°C, dc = 1.591 g/cm3, μ = 51.21 cm-1; 3029 reflections, R = 0.039 and Rw = 0.036. Decomposition studies of 6 established two competing reaction pathways. C-N and Ir-C bond breaking, the microscopic reverse of the formation of 6, gave norbornylene and a reactive Ir intermediate. The competing pathway of C-H reductive elimination occurs by prior ligand dissociation and yields the amination product, exo-2-(phenylamino)norbornane (7). Labeling studies indicated an overall cis addition of the N-H group across the exo face of norbornylene. The individual steps for this reaction were elaborated into a catalytic cycle for the addition of aniline to norbornylene and a mechanism based on these individual steps proposed.

Original languageEnglish
Pages (from-to)6738-6744
Number of pages7
JournalJournal of the American Chemical Society
Volume110
Issue number20
Publication statusPublished - 1988

Fingerprint

Aniline
Catalysis
Chemical activation
Amination
Olefins
Alkenes
Norbornanes
Hydrides
Labeling
Nuclear magnetic resonance spectroscopy
Transition metals
Demonstrations
X-Ray Diffraction
Ligands
Single crystals
Decomposition
X ray diffraction
Magnetic Resonance Spectroscopy
Crystals
Catalysts

ASJC Scopus subject areas

  • Chemistry(all)

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Rational design in homogeneous catalysis. Ir(I)-catalyzed addition of aniline to norbornylene via N-H activation. / Milstein, David; Calabrese, Joseph C.; Milstein, David.

In: Journal of the American Chemical Society, Vol. 110, No. 20, 1988, p. 6738-6744.

Research output: Contribution to journalArticle

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abstract = "The first successful demonstration of the amination of an olefin by a transition-metal-catalyzed N-H activation mechanism was accomplished in a stepwise manner with an Ir(I) catalyst and the substrates aniline and norbornylene. The initial N-H oxidative addition step envisioned in such a mechanism was demonstrated for the complexes Ir(PMe3)4PF6, Ir(PMe3)3(C8H14)Cl, and Ir(PEt3)3Cl, all of which gave rise to stable cis anilido hydride complexes when reacted with aniline. The second step olefin insertion, was accomplished from the reaction of Ir(PEt3)2(C2H4)2Cl (1) with aniline and norbornylene. The resulting insertion product, Ir(PEt3)2(NHPhC7H10)(H)Cl (6), was characterized by NMR spectroscopy and single-crystal X-ray diffraction and was found to have an azoiridacyclobutane type structure. The relevant crystal data for 6 are a = 10.702 (3) {\AA}, b = 13.176 (21) {\AA}, c = 19.498 (5) {\AA}, β = 98.61 (2); P21/c, T = -70°C, dc = 1.591 g/cm3, μ = 51.21 cm-1; 3029 reflections, R = 0.039 and Rw = 0.036. Decomposition studies of 6 established two competing reaction pathways. C-N and Ir-C bond breaking, the microscopic reverse of the formation of 6, gave norbornylene and a reactive Ir intermediate. The competing pathway of C-H reductive elimination occurs by prior ligand dissociation and yields the amination product, exo-2-(phenylamino)norbornane (7). Labeling studies indicated an overall cis addition of the N-H group across the exo face of norbornylene. The individual steps for this reaction were elaborated into a catalytic cycle for the addition of aniline to norbornylene and a mechanism based on these individual steps proposed.",
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AB - The first successful demonstration of the amination of an olefin by a transition-metal-catalyzed N-H activation mechanism was accomplished in a stepwise manner with an Ir(I) catalyst and the substrates aniline and norbornylene. The initial N-H oxidative addition step envisioned in such a mechanism was demonstrated for the complexes Ir(PMe3)4PF6, Ir(PMe3)3(C8H14)Cl, and Ir(PEt3)3Cl, all of which gave rise to stable cis anilido hydride complexes when reacted with aniline. The second step olefin insertion, was accomplished from the reaction of Ir(PEt3)2(C2H4)2Cl (1) with aniline and norbornylene. The resulting insertion product, Ir(PEt3)2(NHPhC7H10)(H)Cl (6), was characterized by NMR spectroscopy and single-crystal X-ray diffraction and was found to have an azoiridacyclobutane type structure. The relevant crystal data for 6 are a = 10.702 (3) Å, b = 13.176 (21) Å, c = 19.498 (5) Å, β = 98.61 (2); P21/c, T = -70°C, dc = 1.591 g/cm3, μ = 51.21 cm-1; 3029 reflections, R = 0.039 and Rw = 0.036. Decomposition studies of 6 established two competing reaction pathways. C-N and Ir-C bond breaking, the microscopic reverse of the formation of 6, gave norbornylene and a reactive Ir intermediate. The competing pathway of C-H reductive elimination occurs by prior ligand dissociation and yields the amination product, exo-2-(phenylamino)norbornane (7). Labeling studies indicated an overall cis addition of the N-H group across the exo face of norbornylene. The individual steps for this reaction were elaborated into a catalytic cycle for the addition of aniline to norbornylene and a mechanism based on these individual steps proposed.

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