Pd(0)/PR<sub>3</sub>-Catalyzed Intermolecular Arylation of sp<sup>3</sup> C−H Bonds

Wasa, Masayuki; Engle, Keary M.; Yu, Jin‐Quan

doi:10.1021/ja903573p

Cited by 304 publications

(129 citation statements)

References 23 publications

(13 reference statements)

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“…Thea rylation of amides 127 and 129 with aryl iodides, [59] alkylation of amide 127 with ethyl iodide 57, [60] and alkynylation of amide 132 with alkynyl bromide 107 [61] led to CÀCb ond formation. In these reactions,a mides with or without a substitution are competent substrates,thus providing amethod to functionalize both natural or unnatural amino acids.…”

Section: Carbonyl Groups (Perfluorinated Amides)mentioning

confidence: 99%

Complementary Strategies for Directed C(sp³)−H Functionalization: A Comparison of Transition‐Metal‐Catalyzed Activation, Hydrogen Atom Transfer, and Carbene/Nitrene Transfer

2017

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The functionalization of C(sp3)−H bonds streamlines chemical synthesis by allowing the use of simple molecules and providing novel synthetic disconnections. Intensive recent efforts in the development of new reactions based on C−H functionalization have led to its wider adoption across a range of research areas. This Review discusses the strengths and weaknesses of three main approaches: transition‐metal‐catalyzed C−H activation, 1,n‐hydrogen atom transfer, and transition‐metal‐catalyzed carbene/nitrene transfer, for the directed functionalization of unactivated C(sp3)−H bonds. For each strategy, the scope, the reactivity of different C−H bonds, the position of the reacting C−H bonds relative to the directing group, and stereochemical outcomes are illustrated with examples in the literature. The aim of this Review is to provide guidance for the use of C−H functionalization reactions and inspire future research in this area.

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Section: Carbonyl Groups (Perfluorinated Amides)mentioning

confidence: 99%

Complementary Strategies for Directed C(sp³)−H Functionalization: A Comparison of Transition‐Metal‐Catalyzed Activation, Hydrogen Atom Transfer, and Carbene/Nitrene Transfer

2017

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“…1B) was the design of a ligand that promotes selective mono-arylation of primary C(sp 3 )–H bonds. Our group has recently focused on the development of simple and weakly coordinating auxiliaries, such as N -methoxyamides and perfluorinated arylamides, to direct a wide range of C(sp 3 )–H activation reactions (10, 11). However, to date we have found that the use of these weakly coordinating auxiliaries is incompatible with the functionalization of the C(sp 3 )–H bonds of α-amino acids (10, 11).…”

mentioning

confidence: 99%

Ligand-Controlled C(sp ³ )–H Arylation and Olefination in Synthesis of Unnatural Chiral α–Amino Acids

Li²,

Deng³

et al. 2014

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The development of ligands that can promote selective insertion of a metal into primary or secondary C(sp3)–H bonds is a central challenge in the field of C–H functionalization. Here, we report a rare example of catalyst-controlled primary and secondary C(sp3)–H arylation using two different ligands. Successive application of these ligands enables the sequential hetero-diarylation of an alanine derivative with two different aryl iodides affording a wide range of β-Ar-β-Ar'-α-amino acids with excellent levels of diastereoselectivity (d.r. > 20:1). Both configurations of the β-chiral center can be accessed by choosing the order in which the aryl iodides are installed, thus demonstrating the potential to construct tertiary chiral centers from a simple methyl group. The realization of this reactivity by electronic and steric modulation of the ligands may provide fundamental guidance for the future design of more effective and selective catalysts for C(sp3)–H activation.

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“…However, the substrate scope was limited to aliphatic acids with a β-quaternary centre, due to the well-known Thorpe–Ingold effect in cyclopalladation17, and ratios of mono- to diarylated products in the range 2.5:1 to 5:1 were observed. Thus, the use of various directing groups to achieve regioselective β-C( sp 3 )–H bond functionalization of carboxylic acid derivatives18192021222324252627282930313233343536373839404142434445 has been extensively explored in the past decades (Fig. 1).…”

mentioning

confidence: 99%

“…Yu's group also demonstrated that mono-coordinated directing groups, such as perfluorinated aryl amides and N -methoxyamide, can effectively direct β-C( sp 3 )-H arylation with the assistance of mono- N -protected amino acid ligands (Fig. 1c)44454647. For example, N -methoxyamide has been used as a directing group4849 for β-C( sp 3 )-H arylation with a pyridine-type ligand, affording various non-natural amino acids from protected alanine derivatives49.…”

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confidence: 99%

Pd-catalysed ligand-enabled carboxylate-directed highly regioselective arylation of aliphatic acids

et al. 2017

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α-amino acids bearing aromatic side chains are important synthetic units in the synthesis of peptides and natural products. Although various β-C-H arylation methodologies for amino acid derivatives involving the assistance of directing groups have been extensively developed, syntheses that directly employ N-protected amino acids as starting materials remain rare. Herein, we report an N-acetylglycine-enabled Pd-catalysed carboxylate-directed β-C(sp3)-H arylation of aliphatic acids. In this way, various non-natural amino acids can be directly prepared from phthaloylalanine in one step in good to excellent yields. Furthermore, a series of aliphatic acids have been shown to be amenable to this transformation, affording β-arylated propionic acid derivatives in moderate to good yields. More importantly, this ligand-enabled direct β-C(sp3)-H arylation could be easily scaled-up to 10 g under reflux conditions, highlighting the potential utility of this synthetic method.

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Pd(0)/PR₃-Catalyzed Intermolecular Arylation of sp³ C−H Bonds

Abstract: Pd(0)-catalyzed intermolecular arylation of sp 3

Cited by 304 publications

References 23 publications

Complementary Strategies for Directed C(sp³)−H Functionalization: A Comparison of Transition‐Metal‐Catalyzed Activation, Hydrogen Atom Transfer, and Carbene/Nitrene Transfer

Complementary Strategies for Directed C(sp³)−H Functionalization: A Comparison of Transition‐Metal‐Catalyzed Activation, Hydrogen Atom Transfer, and Carbene/Nitrene Transfer

Ligand-Controlled C(sp ³ )–H Arylation and Olefination in Synthesis of Unnatural Chiral α–Amino Acids

Pd-catalysed ligand-enabled carboxylate-directed highly regioselective arylation of aliphatic acids

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Pd(0)/PR3-Catalyzed Intermolecular Arylation of sp3 C−H Bonds

Abstract: Pd(0)-catalyzed intermolecular arylation of sp 3

Cited by 304 publications

References 23 publications

Complementary Strategies for Directed C(sp3)−H Functionalization: A Comparison of Transition‐Metal‐Catalyzed Activation, Hydrogen Atom Transfer, and Carbene/Nitrene Transfer

Complementary Strategies for Directed C(sp3)−H Functionalization: A Comparison of Transition‐Metal‐Catalyzed Activation, Hydrogen Atom Transfer, and Carbene/Nitrene Transfer

Ligand-Controlled C(sp 3 )–H Arylation and Olefination in Synthesis of Unnatural Chiral α–Amino Acids

Pd-catalysed ligand-enabled carboxylate-directed highly regioselective arylation of aliphatic acids

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Pd(0)/PR₃-Catalyzed Intermolecular Arylation of sp³ C−H Bonds

Complementary Strategies for Directed C(sp³)−H Functionalization: A Comparison of Transition‐Metal‐Catalyzed Activation, Hydrogen Atom Transfer, and Carbene/Nitrene Transfer

Complementary Strategies for Directed C(sp³)−H Functionalization: A Comparison of Transition‐Metal‐Catalyzed Activation, Hydrogen Atom Transfer, and Carbene/Nitrene Transfer

Ligand-Controlled C(sp ³ )–H Arylation and Olefination in Synthesis of Unnatural Chiral α–Amino Acids