Phosphorus-Containing Groups Assisted Transition Metal Catalyzed C-H Activation Reactions

Over the last few decades, transition metal-catalyzed direct C-H activation with the assistance of a coordinating directing group has emerged as an atom- and stepeconomical synthetic tools to transform C–H bonds into carbon-carbon or carbonheteroatom bonds. Although the strategies involving regioselective C–H cleavage assisted by various directing groups have been extensively reviewed in the literature, we now attempt to give an overview of the recent advances on phosphorus-containing functional group assisted C-H activation reactions catalyzed by transition-metal catalysts including mechanistic study and synthetic applications. The discussion is directed towards C-H olefination, C-H activation/cyclization, C-H arylation, C-H amination, C-H hydroxylation and acetoxylation as well as miscellaneous C-H activation.

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Directing-Group-Assisted Transition-Metal-Catalyzed Direct C–H Oxidative Annulation of Arenes with Alkynes for Facile Construction of Various Oxygen Heterocycles

Synthesis ◽

10.1055/s-0039-1690816 ◽

2020 ◽

Vol 52 (07) ◽

pp. 993-1006 ◽

Cited By ~ 3

Author(s):

Guanghua Kuang ◽

Guangyuan Liu ◽

Xingxing Zhang ◽

Naihao Lu ◽

Yiyuan Peng ◽

...

Keyword(s):

Transition Metal ◽

Noble Metals ◽

Metal Catalysts ◽

Transition Metal Catalysts ◽

Research Papers ◽

Recent Advances ◽

Oxygen Heterocycles ◽

Directing Group ◽

Transition Metal Catalyzed ◽

Metal Catalyzed

The most recent advances in the construction of oxygen heterocycles by the directing-group-assisted transition-metal-catalyzed direct oxidative annulation of arenes with diverse alkynes are summarized in this review. More than 140 recent research papers and many closely related reviews are referenced in this paper. Nine different oxygen heterocycles frameworks are discussed. Several traditional transition-metal catalysts as well as some classical non-noble metals are utilized to promote the annulation. Three plausible controlling models are disclosed to clarify the excellent regioselectivity outcomes achieved in case of unsymmetrical alkyne substrates.1 Introduction2 Coumarins3 I socoumarins and Their Analogues4 2-Pyrones and Their Analogues5 Chromones and Chroman-4-ones6 Chromenes and Isochromenes7 Fused Polycyclic Oxygen Heteroaromatics8 Benzofurans, Dihydrobenzofurans, and Furans9 Phthalides and Benzofuranones10 Benzoxepines11 Conclusion

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Weinreb Amides as Directing Groups for Transition Metal-Catalyzed C-H Functionalizations

Molecules ◽

10.3390/molecules24050830 ◽

2019 ◽

Vol 24 (5) ◽

pp. 830 ◽

Cited By ~ 12

Author(s):

Jagadeesh Kalepu ◽

Lukasz Pilarski

Keyword(s):

Transition Metal ◽

Functional Group ◽

Metal Catalysts ◽

Mechanistic Studies ◽

Weinreb Amides ◽

Transition Metal Catalyzed ◽

Metal Catalyzed

Weinreb amides are a privileged, multi-functional group with well-established utility in classical synthesis. Recently, several studies have demonstrated the use of Weinreb amides as interesting substrates in transition metal-catalyzed C-H functionalization reactions. Herein, we review this part of the literature, including the metal catalysts, transformations explored so far and specific insights from mechanistic studies.

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Recent Advances in Transition Metal-Catalyzed Reactions of Oxabenzonorbornadiene

Current Organic Synthesis ◽

10.2174/1570179416666181122094643 ◽

2019 ◽

Vol 16 (4) ◽

pp. 460-484 ◽

Cited By ~ 11

Author(s):

Rebecca Boutin ◽

Samuel Koh ◽

William Tam

Keyword(s):

Transition Metal ◽

Structural Features ◽

Metal Catalysts ◽

Single Step ◽

Transition Metal Catalysts ◽

Biologically Active ◽

Transition Metal Catalyzed ◽

Catalyzed Reactions ◽

Metal Catalyzed ◽

Work Done

Background: Oxabenzonorbornadiene (OBD) is a useful synthetic intermediate capable of undergoing multiple types of transformations due to three key structural features: a free alkene, a bridged oxygen atom, and a highly strained ring system. Most notably, ring-opening reactions of OBD using transition metal catalysts and nucleophiles produce multiple stereocenters in a single step. The resulting dihydronaphthalene framework is found in many natural products, which have been shown to be biologically active. Objective: This review will provide an overview of transition metal-catalyzed reactions from the past couple of years including cobalt, copper, iridium, nickel, palladium and rhodium- catalyzed reactions. In addition, the recent derivatization of OBD to cyclopropanated oxabenzonorbornadiene and its reactivity will be discussed. Conclusion: It can be seen from the review, that the work done on this topic has employed the use of many different transition metal catalysts, with many different nucleophiles, to perform various transformations on the OBD molecule. Additionally, depending on the catalyst and ligand used, the stereo and regioselectivity of the product can be controlled, with proposed mechanisms to support the understanding of such reactions. The use of palladium has also generated a cyclopropanated OBD, with reactivity similar to that of OBD. An additional reactive site exists at the distal cyclopropane carbon, giving rise to three types of ring-opened products.

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Cu(I)-Bis(phosphine) Dioxides as catalysts for the Enantioselective α-Arylation of Carbonyl Compounds

Synlett ◽

10.1055/a-1503-7339 ◽

2021 ◽

Author(s):

Margarita Escudero-Casao ◽

Giulia Licini ◽

Manuel Orlandi

Keyword(s):

Reaction Mechanism ◽

Transition Metal ◽

Catalytic System ◽

Carbonyl Compounds ◽

Research Area ◽

Metal Catalysts ◽

Transition Metal Catalysts ◽

Transition Metal Catalyzed ◽

Metal Catalyzed

The transition metal catalyzed α-arylation of carbonyl compounds was first reported by Buchwald and Hartwig in 1997. This transformation has been used and studied extensively over the last two decades. Enantioselective variants were also developed that allow for controlling the product stereochemistry. However, these suffer several limitations in the context of formation of tertiary stereocenters. Presented here is our group’s contribution to this research area. The chiral Cu-bis(phosphine) dioxides catalytic system that we reported allowed accessing the enantioselective α-arylation of ketones that were not suitable for this transformation before in good yields and er up to 97.5:2.5. Preliminary insight and speculation concerning the reaction mechanism involving the unusual pairing of bis(phosphine) dioxides with transition metal catalysts is also given.

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A Review on Sulfur-Directed C−H Bond Activation

Mini-Reviews in Organic Chemistry ◽

10.2174/1570193x17999201113142442 ◽

2020 ◽

Vol 17 ◽

Author(s):

Xuchong Tang ◽

Yingwei Zhao

Keyword(s):

Transition Metal ◽

Electron Donor ◽

Bond Activation ◽

Bond Formation ◽

Metal Catalysts ◽

Transition Metal Catalysts ◽

Directing Group ◽

Metal Catalyzed ◽

Sulfur Containing

: Transition-metal-catalyzed C−H bond activation employing a directing group is becoming a powerful tool to access C−C or C−hetero bond formation. Oxygen and nitrogen atoms are commonly applied as the electron donor for these directing groups. In contrast, there are only few studies on sulfur-containing groups, probably due to their toxicity to transition-metal catalysts. Nowadays a large amount of C−H activation reactions directed by sulfur-containing auxiliary groups have been successfully achieved. Because these groups can be facilely removed or modified in situ or in further steps, they are of great value in creative synthetic strategies. This paper reviews recent advances in the studies using thioether, thiol/thiophenol/disulfide, sulfoxide, and thiocarbonyl as directing groups for intermolecular C−H functionalizations as well as intramolecular oxidative annulations.

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Recent Advances in the Synthesis of Acyl Fluorides

Synthesis ◽

10.1055/s-0040-1705951 ◽

2020 ◽

Author(s):

Marie Gonay ◽

Chloé Batisse ◽

Jean-François Paquin

Keyword(s):

Transition Metal ◽

Organic Synthesis ◽

Peptide Synthesis ◽

Uranium Hexafluoride ◽

Metal Catalysts ◽

Recent Advances ◽

Transition Metal Catalyzed ◽

Metal Catalyzed ◽

Nucleophilic Fluorination ◽

Bromine Trifluoride

AbstractAcyl fluorides are valuable intermediates in organic synthesis. They are increasingly employed in peptide synthesis, in challenging esterification and amidation reactions or in transition-metal-catalyzed transformations. This review summarizes recent advances in their preparation.1 Introduction2 Nucleophilic Fluorination2.1 α-Fluoroamine Reagents2.2 Sulfur-Based Reagents2.3 Metal Catalysts2.4 Phosphorus-Based Reagents2.5 N,N′-Dicyclohexylcarbodiimide/HF·Pyridine2.6 Uranium Hexafluoride2.7 Bromine Trifluoride3 Radical Fluorination4 Conclusion

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Silicon Grignard Reagents as Nucleophiles in Transition-Metal-Catalyzed Allylic Substitution

Synthesis ◽

10.1055/s-0037-1610309 ◽

2018 ◽

Vol 51 (01) ◽

pp. 233-239 ◽

Cited By ~ 9

Author(s):

Weichao Xue ◽

Martin Oestreich

Keyword(s):

Transition Metal ◽

Metal Catalysts ◽

Transition Metal Catalysts ◽

Grignard Reagents ◽

Allylic Substitution ◽

Substitution Reactions ◽

Cyclic System ◽

Leaving Group ◽

Transition Metal Catalyzed ◽

Metal Catalyzed

A broad range of transition-metal catalysts is shown to promote allylic substitution reactions of allylic electrophiles with silicon Grignard reagents. The procedure was further elaborated for CuI as catalyst. The regioselectively is independent of the leaving group for primary allylic precursors, favoring α over γ. The stereochemical course of this allylic transposition was probed with a cyclic system, and anti-diastereoselectivity was obtained.

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Recent advances in transition-metal-catalyzed intermolecular carbomagnesiation and carbozincation

Beilstein Journal of Organic Chemistry ◽

10.3762/bjoc.9.34 ◽

2013 ◽

Vol 9 ◽

pp. 278-302 ◽

Cited By ~ 55

Author(s):

Kei Murakami ◽

Hideki Yorimitsu

Keyword(s):

Transition Metal ◽

Transition Metals ◽

Recent Advances ◽

Group 3 ◽

Directing Group ◽

Transition Metal Catalyzed ◽

Electron Withdrawing Group ◽

Group 2 ◽

Metal Catalyzed ◽

Organozinc Reagents

Carbomagnesiation and carbozincation reactions are efficient and direct routes to prepare complex and stereodefined organomagnesium and organozinc reagents. However, carbon–carbon unsaturated bonds are generally unreactive toward organomagnesium and organozinc reagents. Thus, transition metals were employed to accomplish the carbometalation involving wide varieties of substrates and reagents. Recent advances of transition-metal-catalyzed carbomagnesiation and carbozincation reactions are reviewed in this article. The contents are separated into five sections: carbomagnesiation and carbozincation of (1) alkynes bearing an electron-withdrawing group; (2) alkynes bearing a directing group; (3) strained cyclopropenes; (4) unactivated alkynes or alkenes; and (5) substrates that have two carbon–carbon unsaturated bonds (allenes, dienes, enynes, or diynes).

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Recent Progress on the Synthesis of (Aza)indoles through Oxidative Alkyne Annulation Reactions

Synlett ◽

10.1055/s-0036-1590842 ◽

2017 ◽

Vol 28 (15) ◽

pp. 1867-1872 ◽

Cited By ~ 58

Author(s):

Hai-Chao Xu ◽

Zhong-Wei Hou ◽

Zhong-Yi Mao

Keyword(s):

Transition Metal ◽

Recent Progress ◽

Metal Catalysts ◽

Transition Metal Catalysts ◽

Powerful Method ◽

Transition Metal Catalyzed ◽

Metal Catalyzed

The oxidative [3+2] cycloaddition of alkynes with arylamines is a powerful method for the synthesis of (aza)indoles because it employs unfunctionalized and easily available materials. Herein, recent progress in the synthesis of (aza)indoles through transition metal-catalyzed oxidative [3+2] cycloaddition is highlighted.1 Introduction2 Second-Row Transition-Metal Catalysts3 First-Row Transition-Metal Catalysts4 Summary

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