Toolbox for Distal C–H Bond Functionalizations in Organic Molecules

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(6), P. 5682 - 5841

Published: Oct. 18, 2021

Transition-metal-catalyzed C–H activation has developed a contemporary approach to the omnipresent area of retrosynthetic disconnection. Scientific researchers have been tempted take help this methodology plan their synthetic discourses. This paradigm shift helped in development industrial units as well, making synthesis natural products and pharmaceutical drugs step-economical. In vast zone bond activation, functionalization proximal bonds gained utmost popularity. Unlike bonds, distal is more strenuous requires distinctly specialized techniques. review, we compiled various methods adopted functionalize mechanistic insights within each these procedures, scope methodology. With give complete overview expeditious progress made field organic chemistry while also highlighting its pitfalls, thus leaving open for further modifications.

Language: Английский

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Arene diversification through distal C(sp ² )−H functionalization

Science, Journal Year: 2021, Volume and Issue: 372(6543)

Published: May 13, 2021

Transition metal-catalyzed aryl C-H activation is a powerful synthetic tool as it offers step and atom-economical routes to site-selective functionalization. Compared with proximal ortho-C-H activation, distal (meta- and/or para-) remains more challenging due the inaccessibility of these sites in formation energetically favorable organometallic pretransition states. Directing catalyst toward bonds requires judicious template engineering design, well prudent choice ligands. This review aims summarize recent elegant discoveries exploiting directing group assistance, transient mediators or traceless directors, noncovalent interactions, ligand selection control activation.

Language: Английский

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Strategic evolution in transition metal-catalyzed directed C–H bond activation and future directions

Coordination Chemistry Reviews, Journal Year: 2020, Volume and Issue: 431, P. 213683 - 213683

Published: Dec. 9, 2020

Language: Английский

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Access to the meta position of arenes through transition metal catalysed C–H bond functionalisation: a focus on metals other than palladium

Chemical Society Reviews, Journal Year: 2017, Volume and Issue: 47(1), P. 149 - 171

Published: Oct. 26, 2017

The elaboration of simple arenes in order to access more complex substitution patterns is a crucial endeavor for synthetic chemists, given the central role that aromatic rings play all manner important molecules. Classical methods are now routinely used alongside stoichiometric organometallic approaches and, most recently, transition metal catalysis range methodologies available elaborate arene C-H bonds. Regioselectivity an consideration when selecting method those available, it arguably target meta position fewest number. rapid development metal-catalysed bond functionalisation over last few decades has opened new possibilities meta-selective through diverse reactivity metals and their compatibility with wide directing groups. pace discovery such processes grown rapidly five years particular purpose this review examine these but doing so place focus on other than palladium, specific contributions which have been very recently reviewed elsewhere. It hoped will serve highlight reader breadth current strategies mechanisms tackle challenge, may inspire further progress field.

Language: Английский

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Metal-catalysed C–H bond activation and borylation

Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 51(12), P. 5042 - 5100

Published: Jan. 1, 2022

Transition metal-catalysed direct borylation of hydrocarbons via C–H bond activation has received a remarkable level attention as popular reaction in the synthesis organoboron compounds owing to their synthetic versatility.

Language: Английский

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New horizons for catalysis disclosed by supramolecular chemistry

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(13), P. 7681 - 7724

Published: Jan. 1, 2021

Recent advancements in supramolecular catalysis are reviewed, which show the potential of related tools when applied to organic synthesis. Such recognized as innovative instruments that can pave way alternative synthetic strategies.

Language: Английский

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Iridium‐Catalysed C−H Borylation of Heteroarenes: Balancing Steric and Electronic Regiocontrol

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 60(6), P. 2796 - 2821

Published: March 23, 2020

The iridium-catalysed borylation of aromatic C−H bonds has become the preferred method for synthesis organoboron compounds. reaction is highly efficient, tolerant a broad range substituents and can be applied to both carbocyclic heterocyclic substrates. regioselectivity activation dominated by steric considerations there have been considerable efforts develop more selective processes less constrained However, most these focused on benzenoid-type substrates in contrast, heteroarenes remain much desired but challenging with position and/or nature heteroatom(s) significantly affecting reactivity regioselectivity. This review will survey heteroarenes, focusing influence electronic effects regiochemical outcome and, linking current mechanistic understandings, provide insights what currently possible where further developments are required.

Language: Английский

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Transition metal–catalyzed remote C─H borylation: An emerging synthetic tool

Science Advances, Journal Year: 2023, Volume and Issue: 9(16)

Published: April 21, 2023

Transition metal–catalyzed C─H bond activation and borylation is a powerful synthetic method that offers versatile transformation from organoboron compounds to virtually all other functional groups. Compared the ortho-borylation, remote remains more challenging owing inaccessibility of these bonds. Enforcing metal catalyst toward bonds needs well-judged design through proper ligand development. This review article aims summarize recent discoveries for by employment new catalyst/ligand with help steric ligand, noncovalent interactions. It has been found now takes part in total synthesis natural products shorter route. Whereas, Ir-catalyzed predominant, cobalt also started affect this field sustainable cost-effective

Language: Английский

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Alkyne Linchpin Strategy for Drug:Pharmacophore Conjugation: Experimental and Computational Realization of a Meta-Selective Inverse Sonogashira Coupling

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(8), P. 3762 - 3774

Published: Jan. 7, 2020

The late-stage functionalization (LSF) of pharmaceutical and agrochemical compounds by the site-selective activation C–H bonds provides access to diverse structural analogs expands synthetically-accessible chemical space. We report a LSF strategy that hinges on use an alkyne linchpin assemble conjugates sp2-rich marketed pharmaceuticals agrochemicals with sp3-rich 3D fragments natural products. This is accomplished through template-assisted inverse Sonogashira reaction displays high levels selectivity for meta position. protocol also amenable distal modifications α-amino acids. transformation functionality other functional groups further highlights applicative potential. Computational experimental mechanistic studies shed light detailed mechanism. Turnover-limiting 1,2-migratory insertion bromoalkyne coupling partner occurs after relatively fast activation. While this unselectively, regioconvergence results from one adducts undergoing 1,2-trialkylsilyl migration form alkynylated product. A heterobimetallic Pd–Ag transition structure essential product formation in β-bromide elimination step.

Language: Английский

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Chiral Transient Directing Groups in Transition-Metal-Catalyzed Enantioselective C–H Bond Functionalization

ACS Catalysis, Journal Year: 2020, Volume and Issue: 10(21), P. 12898 - 12919

Published: Oct. 21, 2020

Transition-metal-catalyzed C–H bond functionalization has known a rapid evolution in the last years, offering modern strategies for reaching high molecular complexity step- and atom-economical way. Despite indisputable advances, selectivity issues still remain, given ubiquity of bonds on molecules; thus, several approaches have been developed to tackle this challenge. Among them, use transient directing group emerged as an effective tool, circumventing need extra synthetic steps install then cleave molecule. More recently, strategy successfully applied even more challenging transition-metal-catalyzed enantioselective functionalization. This review will highlight discuss main advances made chiral C(sp2)–H C(sp3)–H by transition-metal catalysis.

Language: Английский

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