Transition-Metal-Catalyzed Silylation and Borylation of C–H Bonds for the Synthesis and Functionalization of Complex Molecules

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(19), P. 11619 - 11663

Published: Sept. 26, 2023

The functionalization of C–H bonds in organic molecules containing functional groups has been one the holy grails catalysis. One synthetically important approach to diverse is catalytic silylation or borylation bonds, which enables a broad array downstream transformations afford structures. Advances both undirected and directed methods for transition-metal-catalyzed have led their rapid adoption early-, mid-, late-stage synthesis complex molecules. In this Review, we review application bioactive molecules, materials, ligands. Overall, aim provide picture state art as applied modification architectures that will spur further development these reactions.

Language: Английский

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Simple Ether‐Directed Enantioselective C(sp³)−H Borylation of Cyclopropanes Enabled by Iridium Catalysis

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(14)

Published: Feb. 10, 2023

Reported here is an efficient and simple ether-directed iridium-catalyzed enantioselective C(sp3 )-H borylation of cyclopropanes. Various functional groups were well-tolerated, affording a vast array chiral cyclopropanes with high enantioselectivities. We also demonstrated that the turnover numbers current reaction could be up to 335.

Language: Английский

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Catalytic Enantioselective Primary C–H Borylation for Acyclic All-Carbon Quaternary Stereocenters

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(2), P. 1635 - 1643

Published: Jan. 5, 2024

Creating a perfect catalyst to operate enzyme-like chiral recognition has been long-sought aim. A challenging example in this context is constructing acyclic all-carbon quaternary stereogenic centers by transition metal-catalyzed enantioselective C–H activation. We now report highly iridium-catalyzed primary borylation of α-all-carbon substituted 2,2-dimethyl amides enabled tailor-made bidentate boryl ligand (CBL). The success the current transformation attributed CBL/iridium catalyst, which confined pocket. This protocol provides diverse array stereocenters with excellent enantiocontrol and distinct structural features. Computational study reveals that steric hindrance CBL could regulate type dominant orbital interaction between substrate, crucial conferring high induction.

Language: Английский

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2-Aminophenanthroline Ligands Enable Mild, Undirected, Iridium-Catalyzed Borylation of Alkyl C–H Bonds

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(11), P. 7124 - 7129

Published: March 8, 2024

The catalytic, undirected borylation of alkyl C–H bonds typically occurs at high reaction temperatures or with excess substrate, both, because the low reactivity bonds. Here we report a new iridium system comprising 2-anilino-1,10-phenanthroline as ligand that catalyzes little to no induction period and rates. This superior activation profile 2-aminophenanthroline-ligated catalysts leads broader scope, including reactions sensitive substrates, such epoxides glycosidic acetals, enhanced diastereoselectivity, higher yields borylated products. These also enable alkanes, amines, ethers room temperature for first time. Mechanistic studies imply facile N-borylation under conditions complexes containing N-boryl aminophenanthrolines are competent precatalysts reaction.

Language: Английский

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P(III)-Directed Asymmetric C–H Arylation toward Planar Chiral Ferrocenes by Palladium Catalysis

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(5), P. 3483 - 3491

Published: Jan. 24, 2024

Planar chiral ferrocenyl phosphines have been employed as highly valuable ligands in metal-catalyzed asymmetric reactions. However, their preparation remains a formidable challenge due to the requirement for intricate, multistep synthetic sequences. In addressing this issue, we developed groundbreaking enantioselective C-H activation strategy facilitated by P(III) directing groups, enabling efficient construction of planar single step. Our innovative approach entails combination palladium catalyst, parent phosphine, and phosphoramidite ligand, leading exceptional reactivity enantioselectivity. Remarkably, these novel exhibit remarkable efficacy silver-catalyzed 1,3-dipolar cycloadditions. We carried out experimental computational studies obtain more comprehensive understanding reaction pathway factors contributing

Language: Английский

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Iridium‐Catalyzed Enantioselective C(sp³)−H Borylation of Aminocyclopropanes

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(19)

Published: Feb. 23, 2022

Abstract Transition‐metal‐catalyzed regio‐ and stereo‐controllable C−H functionalization remains a formidable challenge in asymmetric catalysis. Herein, we disclose the first example of iridium‐catalyzed C(sp 3 )−H borylation aminocyclopropanes by using simple imides as weakly coordinating directing groups under mild reaction conditions. The proceeded via six‐membered iridacycle, affording vast range chiral aminocyclopropyl boronates. current method features broad spectrum functional (36 examples) high enantioselectivities (up to 99 %). We also demonstrated synthetic utility preparative scale borylation, C−B bond transformations, conversion group.

Language: Английский

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General and selective metal-free radical α-C–H borylation of aliphatic amines

Chem, Journal Year: 2022, Volume and Issue: 8(11), P. 3096 - 3108

Published: Aug. 22, 2022

Language: Английский

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Ir-Catalyzed Ligand-Free Directed C–H Borylation of Arenes and Pharmaceuticals: Detailed Mechanistic Understanding

The Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 87(6), P. 4360 - 4375

Published: March 7, 2022

An efficient method for Ir-catalyzed ligand free ortho borylation of arenes (such as, 2-phenoxypyridines, 2-anilinopyridines, benzylamines, benzylpiperazines, benzylmorpholines, benzylpyrrolidine, benzylpiperidines, benzylazepanes, α-amino acid derivatives, aminophenylethane and other important scaffolds) pharmaceuticals has been developed. The reaction underwent via an interesting mechanistic pathway, as revealed by the detailed investigations using kinetic isotope studies DFT calculations. catalytic cycle is found to involve intermediacy Ir-boryl complex where substrate C–H activation turnover determining step, intriguingly without any appreciable primary KIE. displays a broad range scope functional group tolerance. Numerous late-stage various molecules drugs were achieved this developed strategy. borylated compounds further converted into more valuable functionalities. Moreover, utilizing benefit B–N intramolecular interaction mono compounds, operationally simple selective diborylation 2-phenoxypyridines numerous functionalized arenes. Furthermore, synthetic utility showcased with removal pyridyl directing from product achieve phenol along ipso-borylation preparation 1,2-diborylated benzene.

Language: Английский

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Site‐ and Stereoselective C(sp³)−H Borylation of Strained (Hetero)Cycloalkanols Enabled by Iridium Catalysis

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 62(8)

Published: Dec. 30, 2022

Transition metal-catalyzed site- and stereoselective C-H activation of strained (hetero)cycloalkanes remains a formidable challenge. We herein report carbamate-directed iridium-catalyzed asymmetric β-C(sp3 )-H borylation cyclopropanol derivatives. A variety densely functionalized cyclopropanols were obtained in good enantioselectivities via desymmetrization kinetic resolution. In addition, site-selective C(sp3 methine groups furnished α-borylated (hetero)cycloalkanols moderate to yields. The synthetic utility the method was further shown gram-scale synthesis diverse downstream transformations borylated products.

Language: Английский

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Synthesis of Chiral Sulfoximines via Iridium‐Catalyzed Regio‐ and Enantioselective C−H Borylation: A Remarkable Sidearm Effect of Ligand

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 62(6)

Published: Dec. 13, 2022

Transition metal-catalyzed enantioselective C-H activation of prochiral sulfoximines for non-annulated products remains a formidable challenge. We herein report iridium-catalyzed borylation N-silyl diaryl using well-designed chiral bidentate boryl ligand with bulky side arm. This method is capable accommodating broad range substrates under mild reaction conditions, affording vast array high enantioselectivities. also demonstrated the synthetic utility on preparative-scale diverse downstream transformations, including synthesis version bioactive molecules. Computational studies showed that arm confers regio- and enantioselectivity through steric effect.

Language: Английский

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