Ligand‐Promoted Borylation of C(sp<sup>3</sup>)H Bonds with Palladium(II) Catalysts

He, Jian; Jiang, Heng; Takise, Ryosuke; Zhu, Ru‐Yi; Chen, Gang; Dai, Hui‐Xiong; Dhar, T. G. Murali; Shi, Jun; Zhang, Hao; Cheng, Peter T.; Yu, Jin‐Quan

doi:10.1002/ange.201509996

Cited by 51 publications

(14 citation statements)

References 63 publications

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“…Following our previous finding that quinoline and pyridine ligands can accelerate C(sp 3 )–H activation (26) (Fig. 2, L1-3 ), we prepared a number of corresponding chiral ligands including L4 , L5 and examined their activity under standard reaction conditions.…”

Section: Main Textmentioning

confidence: 99%

Ligand-accelerated enantioselective methylene C(sp ³ )–H bond activation

Chen

Gong

Zhuang

et al. 2016

Science

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326

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The development of catalytic enantioselective C(sp3)–H metal insertion reactions has been a significant challenge. Moderate success has recently been achieved via Pd-catalyzed desymmetrization of prochiral C–H bonds located on two different carbon centers. Herein, we report the discovery of chiral acetyl-protected aminoethyl quinoline (APAQ) ligands that enables Pd(II)-catalyzed enantioselective arylation of prochiral methylene C–H bonds on the same carbon center. The feasibility of performing asymmetric Pd insertion into ubiquitous β-methylene C–H bonds of aliphatic amides offers an alternative disconnection for constructing β-chiral centers. Systematic tuning of the ligand structure reveals that a six-membered instead of a five-membered chelation of these types of ligands with the Pd(II) is essential for accelerating the C(sp3)–H activation thereby achieving enantioselectivity.

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Section: Main Textmentioning

confidence: 99%

Ligand-accelerated enantioselective methylene C(sp ³ )–H bond activation

Chen

Gong

Zhuang

et al. 2016

Science

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326

152

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“…These have been prepared via hydroboration of protected allylglycine [121][122][123][124][125], quenching of a lithiated serine analogue with triisopropylborate [126], a Cu-catalyzed cross-coupling of gem-diborylalkanes with primary alkyl halides [127], and very recently by Pd-catalyzed C(sp 3 )-H bond activation (selected examples are shown in Figure 10, left side) [128]. Campbell prepared bishomophenylalanine derivatives 58 by hydroboration of protected allylated oxazolidine 56 with 9-borabicyclo[3,3,1]nonane (9-BBN), followed by Suzuki-Miyaura reaction with aryl iodides and phenyl bromide in good yields ( Figure 10A) [121].…”

Section: Synthesis Of Borylated Aromatic and Aliphatic Amino Acids Anmentioning

confidence: 99%

The Suzuki–Miyaura Cross-Coupling as a Versatile Tool for Peptide Diversification and Cyclization

et al. 2017

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Abstract:The (site-selective) derivatization of amino acids and peptides represents an attractive field with potential applications in the establishment of structure-activity relationships and labeling of bioactive compounds. In this respect, bioorthogonal cross-coupling reactions provide valuable means for ready access to peptide analogues with diversified structure and function. Due to the complex and chiral nature of peptides, mild reaction conditions are preferred; hence, a suitable cross-coupling reaction is required for the chemical modification of these challenging substrates. The Suzuki reaction, involving organoboron species, is appropriate given the stability and environmentally benign nature of these reactants and their amenability to be applied in (partial) aqueous reaction conditions, an expected requirement upon the derivatization of peptides. Concerning the halogenated reaction partner, residues bearing halogen moieties can either be introduced directly as halogenated amino acids during solid-phase peptide synthesis (SPPS) or genetically encoded into larger proteins. A reversed approach building in boron in the peptidic backbone is also possible. Furthermore, based on this complementarity, cyclic peptides can be prepared by halogenation, and borylation of two amino acid side chains present within the same peptidic substrate. Here, the Suzuki-Miyaura reaction is a tool to induce the desired cyclization. In this review, we discuss diverse amino acid and peptide-based applications explored by means of this extremely versatile cross-coupling reaction. With the advent of peptide-based drugs, versatile bioorthogonal conversions on these substrates have become highly valuable.

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“…Unfortunately, the typical C( sp 3 )–H bond is highly inert and thermodynamically stable, requiring eloquent catalytic strategies to activate the bond compared to conventional C–H functionalization methods ,. Transition metal‐catalyzed directed C–H activation has been extensively explored by installing powerful directing groups, and the scope of the transformations can be further expanded through the incorporation of ligands into the catalysis . Recent studies of specific ligand design for coordination with palladium have proved to be critical for C–H activation, and advantageously require less synthetic steps .…”

Section: Introductionmentioning

confidence: 99%

Selective C(sp³)–H Monoarylation Catalyzed by a Covalently Cross‐Linked Reverse Micelle‐Supported Palladium Catalyst

Hoyt

Lee

et al. 2017

Adv Synth Catal

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In this work, we illustrate the performance of as olvated micelle-supported liganda saplatform for coordination with palladium for C-H arylation. Themicelle-supported ligandiso ne of the first applications of am icelle-supported ligand for C-H arylation, andprovides atunable support for future elaboration. Theu se of as patially constrained systemp ro-moted selectivity trends influenced by botht he sterics and electronics of the system, differing from the homogeneous catalyst, with high yields and selectivities.

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Ligand‐Promoted Borylation of C(sp³)H Bonds with Palladium(II) Catalysts

Cited by 51 publications

References 63 publications

Ligand-accelerated enantioselective methylene C(sp ³ )–H bond activation

Ligand-accelerated enantioselective methylene C(sp ³ )–H bond activation

The Suzuki–Miyaura Cross-Coupling as a Versatile Tool for Peptide Diversification and Cyclization

Selective C(sp³)–H Monoarylation Catalyzed by a Covalently Cross‐Linked Reverse Micelle‐Supported Palladium Catalyst

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Ligand‐Promoted Borylation of C(sp3)H Bonds with Palladium(II) Catalysts

Cited by 51 publications

References 63 publications

Ligand-accelerated enantioselective methylene C(sp 3 )–H bond activation

Ligand-accelerated enantioselective methylene C(sp 3 )–H bond activation

The Suzuki–Miyaura Cross-Coupling as a Versatile Tool for Peptide Diversification and Cyclization

Selective C(sp3)–H Monoarylation Catalyzed by a Covalently Cross‐Linked Reverse Micelle‐Supported Palladium Catalyst

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Resources

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Ligand‐Promoted Borylation of C(sp³)H Bonds with Palladium(II) Catalysts

Ligand-accelerated enantioselective methylene C(sp ³ )–H bond activation

Ligand-accelerated enantioselective methylene C(sp ³ )–H bond activation

Selective C(sp³)–H Monoarylation Catalyzed by a Covalently Cross‐Linked Reverse Micelle‐Supported Palladium Catalyst