Platinum-catalyzed direct amination of allylic alcohols under mild conditions: Ligand and microwave effects, substrate scope, and mechanistic study

Takashi Ohshima, Yoshiki Miyamoto, Junji Ipposhi, Yasuhito Nakahara, Masaru Utsunomiya, Kazushi Mashima

Research output: Contribution to journalArticle

121 Citations (Scopus)

Abstract

Transition metal-catalyzed amination of allylic compounds via a π-allylmetal intermediate is a powerful and useful method for synthesizing allylamines. Direct catalytic substitution of allylic alcohols, which forms water as the sole coproduct, has recently attracted attention for its environmental and economical advantages. Here, we describe the development of a versatile direct catalytic amination of both aryl- and alkyl-substituted allylic alcohols with various amines using Pt-Xantphos and Pt-DPEphos catalyst systems, which allows for the selective synthesis of various monoallylamines, such as the biologically active compounds Naftifine and Flunarizine, in good to high yield without need for an activator. The choice of the ligand was crucial toward achieving high catalytic activity, and we demonstrated that not only the large bite-angle but also the linker oxygen atom of the Xantphos and DPEphos ligands was highly important. In addition, microwave heating dramatically affected the catalyst activity and considerably decreased the reaction time compared with conventional heating. Furthermore, several mechanistic investigations, including 1H and 31P{1H} NMR studies; isolation and characterization of several catalytic intermediates, Pt(xantphos)Cl2, Pt(η2-C3H5OH)(xantphos), etc; confirmation of the structure of [Pt(η3-allyl)(xantphos)]OTf by X-ray crystallographic analysis; and crossover experiments, suggested that formation of the π-allylplatinum complex through the elimination of water is an irreversible rate-determining step and that the other processes in the catalytic cycle are reversible, even at room temperature.

Original languageEnglish
Pages (from-to)14317-14328
Number of pages12
JournalJournal of the American Chemical Society
Volume131
Issue number40
DOIs
Publication statusPublished - Oct 14 2009

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Amination
Microwaves
Platinum
Catalyst activity
Alcohols
Ligands
Microwave heating
Substrates
Transition metals
Water
Amines
Substitution reactions
Heating
Nuclear magnetic resonance
X rays
Atoms
Catalysts
Oxygen
Allylamine
Flunarizine

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Platinum-catalyzed direct amination of allylic alcohols under mild conditions : Ligand and microwave effects, substrate scope, and mechanistic study. / Ohshima, Takashi; Miyamoto, Yoshiki; Ipposhi, Junji; Nakahara, Yasuhito; Utsunomiya, Masaru; Mashima, Kazushi.

In: Journal of the American Chemical Society, Vol. 131, No. 40, 14.10.2009, p. 14317-14328.

Research output: Contribution to journalArticle

Ohshima, Takashi ; Miyamoto, Yoshiki ; Ipposhi, Junji ; Nakahara, Yasuhito ; Utsunomiya, Masaru ; Mashima, Kazushi. / Platinum-catalyzed direct amination of allylic alcohols under mild conditions : Ligand and microwave effects, substrate scope, and mechanistic study. In: Journal of the American Chemical Society. 2009 ; Vol. 131, No. 40. pp. 14317-14328.
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