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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Facile Access to Cyclopropylboronates via Stereospecific Deborylative Cyclization: A Leaving Group‐Assisted Activation of Geminal Diborons

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(21)

Published: March 24, 2023

Herein we reported a transition metal-free deborylative cyclization strategy, based on which two routes have been developed, generating racemic and enantioenriched cyclopropylboronates. The of geminal-bis(boronates) bearing leaving group was highly diastereoselective, tolerating few functional groups applicable to heterocycles. When optically active epoxides were used as the starting materials, cyclopropylboronates could be efficiently prepared with >99 % stereospecificity. Mechanistic studies showed that at γ-position played crucial role significantly promoted activation gem-diboron moiety.

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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Advances in the Synthesis of Cyclopropylamines

Chemical Reviews, Journal Year: 2025, Volume and Issue: unknown

Published: March 6, 2025

Cyclopropylamines are an important subclass of substituted cyclopropanes that combine the unique electronic and steric properties with presence a donor nitrogen atom. In addition to their in diverse array biologically active compounds, cyclopropylamines utilized as synthetic intermediates, particularly ring-opening or cycloaddition reactions. Consequently, synthesis these compounds has constituted significant research topic, evidenced by abundant published methods. widely used Curtius rearrangement, classical cyclopropanation methods have been adapted integrate function (Simmons-Smith reaction, metal-catalyzed reaction diazo on olefins, Michael-initiated ring-closure reactions) advances enantioselective synthesis. More recently, specific developed for preparation aminocyclopropane moiety (Kulinkovich reactions applied amides nitriles, cyclopropenes, involving C-H functionalization, ...). The topic this review is present different cyclopropylamine derivatives, aim covering methodological best possible, highlighting scope, stereochemical aspects future trends.

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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Enantioselective Suzuki cross-coupling of 1,2-diboryl cyclopropanes

Chemical Science, Journal Year: 2023, Volume and Issue: 14(6), P. 1575 - 1581

Published: Jan. 1, 2023

Herein, we describe the catalytic enantioselective cross-coupling of 1,2-bisboronic esters. Prior work on group specific cross coupling is limited to use geminal bis-boronates. This desymmetrization provides a novel approach prepare enantioenriched cyclopropyl boronates with three contiguous stereocenters, that could be further derivatized through selective functionalization carbon-boron bond. Our results suggest transmetallation, which enantiodetermining step, takes place retention stereochemistry at carbon.

Language: Английский

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An Iridium/Aluminum Cooperative Strategy for the β‐C(sp³)‐H Borylation of Saturated Cyclic Amines

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(23)

Published: March 29, 2023

Despite the widespread success in functionalization of C(sp2 )-H bonds, deliberate C(sp3 bonds a highly site- and stereoselective manner remains longstanding challenge. Herein, we report an iridium/aluminum cooperative catalytic system that enables β-selective C-H borylation saturated cyclic amines lactams. Furthermore, have accomplished enantioselective variant using binaphthol-derived chiral aluminum catalysts to forge C-B with high levels stereocontrol. Computational studies suggest formation Lewis pair substrates is crucial lower energy transition state for rate-determining reductive elimination step.

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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