Palladium/Norbornene‐Mediated Tandem CH Amination/CI Alkenylation Reaction of Aryl Iodides with Secondary Cyclic <i>O</i>‐Benzoyl Hydroxylamines and Activated Terminal Olefins

Chen, Zhiyuan; Ye, Changqing; Zhu, Hai‐Liang; Zeng, Xing‐Ping; Yuan, Jianjun

doi:10.1002/chem.201400084

Cited by 87 publications

(32 citation statements)

References 128 publications

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“…28 Chen also applied a similar protocol for the synthesis of biaryl amines 31, replacing olefins with pinacol boronates 30 ( Figure 9B). 29 Liang and Xu reported an ortho-amination reaction using N-benzoyloxyamines 27 followed by alkenylation at the ipso carbon by a Pd carbene generated from tosylhydrazone 32.…”

Section: Aromatic Aminationmentioning

confidence: 97%

Pd/Norbornene: A Winning Combination for Selective Aromatic Functionalization via C–H Bond Activation

et al. 2016

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Direct C-H bond activation is an important reaction in synthetic organic chemistry. This methodology has the potential to simplify reactions by avoiding the use of prefunctionalized reagents. However, selectivity, especially site selectivity, remains challenging. Sequential reactions, in which different molecules or groups are combined in an ordered sequence, represent a powerful tool for the construction of complex molecules in a single operation. We have discovered and developed a synthetic methodology that combines selective C-H bond activation with sequential reactions. This procedure, which is now known as the "Catellani reaction", enables the selective functionalization of both the ortho and ipso positions of aryl halides. The desired molecules are obtained with high selectivity from a pool of simple precursors. These molecules are assembled under the control of a palladacycle, which is formed through the joint action of a metal (Pd) and an olefin such as norbornene. These two species act cooperatively with an aryl halide to construct the palladacycle, which is formed through ortho-C-H activation of the original aryl halide. The resulting complex acts as a scaffold to direct the reaction (via Pd(IV)) of other species, such as alkyl or aryl halides and amination or acylation agents, toward the sp(2) C-Pd bond. At the end of this process, because of steric hindrance, the scaffold is dismantled by norbornene extrusion. Pd(0) is cleaved from the organic product through C-C, C-H, C-N, C-O, or C-B coupling, in agreement with the well-known reactivity of aryl-Pd complexes. The cycle involves Pd(0), Pd(II), and Pd(IV) species. In particular, our discovery relates to alkylation and arylation reactions. Recently, remarkable progress has been made in the following areas: (a) the installation of an amino or an acyl group at the ortho position of aryl halides, (b) the formation of a C-B bond at the ipso position, (c) the achievement of meta-C-H bond activation of aryl rings bearing a chelating directing group by Pd(II)/Pd(IV)/norbornene catalysis, and (d) the activation of N-H and C-H bonds in sequence for indole 2-alkylation. In this Account, we explain the main features of this methodology, describe its synthetic potential, and illustrate some remarkable progress that has been made, emphasizing the most recent developments and applications in total synthesis.

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Section: Aromatic Aminationmentioning

confidence: 97%

Pd/Norbornene: A Winning Combination for Selective Aromatic Functionalization via C–H Bond Activation

et al. 2016

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“…IR (KBr): 3428, 2984, 1727, 1603, 1238, 1154 3 Hz),117.7,121.6,121.8,126.1,127.6,129.7 (d,3 J CF = 8.2 Hz),129.9,137.7,142.3 (d,3 J CF = 7. 9 Hz),146.9,153.9,163.4 (d,1 (d,J = 8 Hz,1 H),7.82 (d,J = 8 Hz,1 H),7.88 (d,J = 8.4 Hz,2 H). 13 C NMR (100 MHz, CDCl 3 ): δ = 43.8,52.1,108.0,110.9 (d,2 J CF = 22.7 Hz),114.8 (d,2 J CF = 21.4 Hz),117.7,121.6,121.8,126.2,127.6,129.7 (d,3 J CF = 7.…”

Section: Ethyl [3-(3-fluorophenyl)isoquinolin-1-ylamino]acetate (3da)mentioning

confidence: 98%

“…13 C NMR (100 MHz, CDCl 3 ): δ = 14.3, 21.3, 44.0, 61.2, 107.1, 117.3, 121.6, 125.6, 126.3, 126.5, 127.5, 129.2, 129.8, 137.1, 138.0, 148.5, 153.8, 171.9. 3, 43.9, 52.1, 107.2, 117.3, 121.6, 125.6, 126.5, 127.5, 129.0, 129.2, 129.8, 137.1, 138.0, 148.5, 153.7, 172 (d,J = 8.4 Hz,1 H),7.86 (d,J = 8.4 Hz,1 H),8.11 (d,J = 8.8 Hz,2 H). 13 C NMR (100 MHz, CDCl 3 ): δ = 14.…”

Section: Ethyl (3-p-tolylisoquinolin-1-ylamino)acetate (3ba)mentioning

confidence: 98%

“…9 Hz),130.0,137.8,142.3 (d,3 J CF = 7. 8 Hz),147.0,153.8,163.3 (d,1 (d,J = 5.2 Hz,2 H),5.94 (br s,1 H),7.14 (t,J = 8.4 Hz,2 H),7.41 (d,J = 10.8 Hz,2 H),7.56 (t,J = 7.2 Hz,1 H),7.70 (t,J = 8.4 Hz,1 H),7.82 (t,J = 8.4 Hz,1 H),8.12 (t,J = 8.4 Hz,2 H). 13 C NMR (100 MHz, CDCl 3 ): δ = 14.2,44.0,61.2,107.2,115.2 (d,2 J CF = 21 Hz),117.3,121.6,125.8,127.5,128.2 (d,3 J CF = 8.2 Hz),129.9,135.9,137.9,147.5,153.8,163.1 (d,1 …”

Section: Ethyl [3-(3-fluorophenyl)isoquinolin-1-ylamino]acetate (3da)mentioning

confidence: 99%

“…IR (KBr): 3426, 2985, 1727, 1603, 1276, 1154 (d,J = 8 Hz,1 H),7.82 (d,J = 8.4 Hz,1 H),8.07 (d,J = 7.8 Hz,2 H). 13 C NMR (100 MHz, CDCl 3 ): δ = 14.3, 21.3, 44.0, 61.2, 107.1, 117.3, 121.6, 125.6, 126.3, 126.5, 127.5, 129.2, 129.8, 137.1, 138.0, 148.5, 153.8, 171.9.…”

Section: Ethyl (3-p-tolylisoquinolin-1-ylamino)acetate (3ba)mentioning

confidence: 99%

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Synthesis of 1-Aminoisoquinolines via the Coinage Metal Cocatalyzed Reaction of 2-Alkynylbenzaldoximes with Isocyanoacetates

Wang

et al. 2014

Synthesis

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An efficient reaction of 2-alkynylbenzaldoximes with 2-isocyanoacetates cocatalyzed by silver triflate and gold(I) chloride is described, providing 1-aminoisoquinolines in good to excellent yields under mild conditions. Mechanistic experiments suggest that the gold(I) cation might play a crucial role in the activation of the isocyanide substrate. The observed reactivity and the unique pathway of substrate activation in the cocatalyzed processes are quite informative for further study.Isoquinoline nuclei are key components of pharmacophores, natural products, and versatile synthetic building blocks. 1 In particular, 1-aminoisoquinoline derivatives have been found to act as efficacious inhibitors of mutant B-Raf enzyme, 2 PDE4, 3 adenosine A3 receptor, 4 and dopamine D2 and D3 receptors. 5 In addition, they also exhibit strong cytotoxic activity against different human cancer cell lines. 6 Consequently, continuous effort has been given to the development of methods for the rapid synthesis of these nitrogen-containing heterocycles in both academic and industrial laboratories. Typical 1-aminoisoquinolines are usually prepared starting from haloisoquinolines or metalated isoquinolines. 7 However, this 'prefunctionalization' strategy is obviously hindered by the extra preparation efforts to obtain the precursors and the formation of stoichiometric byproducts. Transition-metal-catalyzed C-N bond-formation reactions, which are represented by Buchwald-Hartwig 8 or Ullmanntype 9 amination reactions, are highly versatile, but several instances continue to pose challenges since the transformations need relatively expensive metal catalysts and ligands, or crucial inert conditions. Although much effort has been invested in the synthesis of functionalized isoquinoline derivatives, the preparation of specific 1-aminoisoquinolines remains highly desirable in synthetic organic chemistry. Thus, there is still an urgent need to develop new strategies for the rapid generation of diversified aminoisoquinoline derivatives under gentle conditions. Transition-metal-catalyzed domino reactions have been well recognized as an efficient synthetic tool because they can provide straightforward access to structurally diverse molecules in a one-pot reaction process. 10,11 For example, Wu and co-workers have described a novel silver triflate catalyzed/phosphonium salt promoted reaction of 2-alkynylbenzaldoximes with amines for the preparation of 1-aminoisoquinoline derivatives. 12 The reaction relies on silver triflate as an effective catalyst for the formation of the isoquinoline framework, and phosphonium salt as an

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Palladium( II ) acetate – tertiary phosphine

Ho¹

2017

Fieser and Fieser's Reagents for Organic Synthesis

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Palladium/Norbornene‐Mediated Tandem CH Amination/CI Alkenylation Reaction of Aryl Iodides with Secondary Cyclic O‐Benzoyl Hydroxylamines and Activated Terminal Olefins

Abstract: A novel palladium-catalyzed norbornene-mediated three-component reaction for the construction of ortho-alkenyl aromatic tertiary amines has been achieved, which represents a useful extension of the Catellani-type tandem ortho-selective CH amination transformations.

Cited by 87 publications

References 128 publications

Pd/Norbornene: A Winning Combination for Selective Aromatic Functionalization via C–H Bond Activation

Pd/Norbornene: A Winning Combination for Selective Aromatic Functionalization via C–H Bond Activation

Synthesis of 1-Aminoisoquinolines via the Coinage Metal Cocatalyzed Reaction of 2-Alkynylbenzaldoximes with Isocyanoacetates

Palladium( II ) acetate – tertiary phosphine

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