Development and Understanding of Late Transition Metal-catalyzed Intermolecular Hydroamination of Conjugated Olefins-Days at Hartwig Lab./Yale University-

  • Utsunomiya Masaru
    Mitsubishi Chemical Corporation, Petrochemicals R&TD Division Research Center, C 4 Derivatives Technology Laboratory

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Other Title
  • 共役オレフィン類のヒドロアミノ化反応触媒の開発を通じて学んだこと―Yale大学Hartwig研究室にて―
  • ラウンジ キョウヤク オレフィンルイ ノ ヒドロアミノカ ハンノウ ショクバイ ノ カイハツ オ ツウジテ マナンダ コト Yale ダイガク Hartwig ケンキュウシツ ニテ
  • Days at Hartwig Lab./Yale University
  • -Yale大学Hartwig研究室にて-

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Abstract

Discovery and understanding of late transition metal-catalyzed intermolecular, hydroamination of vinylarenes with various kinds of alkylamines have been performed. Catalysts having palladium, rhodium, and ruthenium as metal center gave hydroamination products with excellent regio selectivity based on the metal feature. In this paper, catalyst development, reaction scope and mechanistic study are briefly summarized for various hydroamination. Palladium catalyst gave Markovnikov product of styrene derivatives with cyclic and acyclic secondary alkylamines. In contrast, rhodium and ruthenium performed anti-Markovnikov hydroamination of vinylarenes to produce various kinds of amines with or without enamine as side product. Finally, catalytic additions of OH bonds of phenols and carboxylic acids across conjugated dienes were achieved by simple palladium catalyst.

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