α‐Difluoroalkylation of Benzyl Amines with Trifluoromethylarenes

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(40)

Published: Aug. 19, 2023

Abstract An α‐difluoroalkylation of benzyl amines with trifluoromethylarenes is disclosed herein. This protocol characterized by its operational simplicity, excellent chemoselectivity and broad scope—even advanced synthetic intermediates—, thus offering a new entry point to medicinally‐relevant α‐difluoroalkylated from simple, yet readily accessible, precursors.

Language: Английский

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Cooperative activation of carbon–hydrogen bonds by heterobimetallic systems

Dalton Transactions, Journal Year: 2023, Volume and Issue: 53(4), P. 1393 - 1409

Published: Dec. 21, 2023

The activation of C–H bonds by heterobimetallic compounds is a rich area research that has recently received increased attention. This perspective highlights recent advances and aims to guide the reader in this rapidly evolving field.

Language: Английский

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Masters of Mediation: MN(SiMe₃)₂ in Functionalization of C(sp³)−H Latent Nucleophiles

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(29)

Published: March 18, 2024

Abstract Organoalkali compounds have undergone a far‐reaching transformation being coupling partner to mediator in unusual organic conversions which finds its spot the field of sustainable synthesis. Transition‐metal catalysis has always been priority C( sp 3 )−H bond functionalization, however alternatively, recent times this seriously challenged by earth‐abundant alkali metals and their complexes arriving at new organometallic reagents. In line, importance MN(SiMe ) 2 (M=Li, Na, K & Cs) reagent revived functionalization over years synthesis is showcased minireview. with higher reactivity, enhanced stability, bespoke cation‐π interaction shown eye‐opening mediated processes such as )−C( cross‐coupling, radical‐radical aminobenzylation, annulation, aroylation, other transformations utilize readily available petrochemical feedstocks. This article also emphasizes reactivity unreactive robust C−X (X=O, N, F, C) cleavage reactions that occurred alongside functionalization. Overall, review encourages community exploit untapped potential inspires them take up subject even greater heights.

Language: Английский

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Alkali‐Metal‐Alkoxide Powered Zincation of Fluoroarenes Employing Zinc Bis‐Amide Zn(TMP)₂

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(29)

Published: March 23, 2023

Reminiscent of Lochmann-Schlosser superbase recipes, the addition two molar equivalents KOtBu to Zn(TMP)2 (TMP=2,2,6,6-tetramethylpiperidide) transforms this mild zinc bis-amide base a powerful metalating agent able perform facile regioselective zincation wide range sensitive fluoroarenes. Structural authentication intermediates post Zn-H exchange demonstrates activation both TMP groups form higher order bis-aryl potassium zincates, isolable as solids and further functionalized in electrophilic interception reactions. Studies assessing role reveal that first equivalent undergoes co-complexation with , enabling kinetic amide groups; whereas second stabilizes metalated intermediate preventing ligand redistribution. Showcasing its power, bimetallic KOtBu/Zn(TMP)2 partnership, can effect toluene benzene at room temperature.

Language: Английский

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Unlocking the Metalation Applications of TMP‐powered Fe and Co(II) bis(amides): Synthesis, Structure and Mechanistic Insights

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(24)

Published: April 2, 2024

Abstract Typified by LiTMP and TMPMgCl.LiCl, (TMP=2,2,6,6‐tetramethylpiperidide), s‐block metal amides have found widespread applications in arene deprotonative metalation. On the contrary, transition lack sufficient basicity to activate these substrates. Breaking new ground this field, here we present synthesis full characterisation of earth‐abundant metals M(TMP) 2 (M=Fe, Co). Uncovering a reactivity profile towards fluoroarenes, amide complexes can promote direct M−H exchange processes regioselectively using one or two their basic arms. Remarkably, even when perfluorinated substrate, selective C‐H metalation occurs leaving C−F bonds intact. Their kinetic be boosted LiCl NBu 4 Cl additives which enables formation kinetically activated ate species. Combining spectroscopic structural studies with DFT calculations, mechanistic insights been gained on how low polarity take place. also used access ferrocene cobaltocene deprotonation cyclopentadiene undergo efficient CO insertion both groups under mild reaction conditions.

Language: Английский

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Applying Na/Co(ii) bimetallic partnerships to promote multiple Co–H exchanges in polyfluoroarenes

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(36), P. 5383 - 5386

Published: Jan. 1, 2023

Heterobimetallic base NaCo(HMDS)3 [HMDS = N(SiMe3)2] enables regioselective di-cobaltation of activated polyfluoroarenes under mild reaction conditions. For 1,3,5-C6H2X3 (X= Cl, F), in excess at 80 °C impressively induces the collective cleavage five bonds (two C-H and three C-X) substrates via a cascade activation process that cannot be replicated by LiCo(HMDS)3 or KCo(HMDS)3.

Language: Английский

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Unlocking the Metalation Applications of TMP‐powered Fe and Co(II) bis(amides): Synthesis, Structure and Mechanistic Insights

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(24)

Published: April 2, 2024

Abstract Typified by LiTMP and TMPMgCl.LiCl, (TMP=2,2,6,6‐tetramethylpiperidide), s‐block metal amides have found widespread applications in arene deprotonative metalation. On the contrary, transition lack sufficient basicity to activate these substrates. Breaking new ground this field, here we present synthesis full characterisation of earth‐abundant metals M(TMP) 2 (M=Fe, Co). Uncovering a reactivity profile towards fluoroarenes, amide complexes can promote direct M−H exchange processes regioselectively using one or two their basic arms. Remarkably, even when perfluorinated substrate, selective C‐H metalation occurs leaving C−F bonds intact. Their kinetic be boosted LiCl NBu 4 Cl additives which enables formation kinetically activated ate species. Combining spectroscopic structural studies with DFT calculations, mechanistic insights been gained on how low polarity take place. also used access ferrocene cobaltocene deprotonation cyclopentadiene undergo efficient CO insertion both groups under mild reaction conditions.

Language: Английский

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Interaction and Energy Decomposition Analyses to Predict Stability of Tetraaryl Square Planar Cobalt Complexes

ChemCatChem, Journal Year: 2023, Volume and Issue: 15(19)

Published: July 26, 2023

Abstract The sodium‐mediated cobaltation of pentafluorobenzene using the bimetallic base [NaCo(HMDS) 3 ] (HMDS=N(SiMe ) 2 has been reported to afford a novel tetraaryl Co(II) square planar complex. Yet, preparation analogue structures with 1,2,3,4‐tetrafluorobenzene, 1,3,5‐trichlorobenzene, and 1,4‐dibromo‐2,5‐difluorobenzene remains elusive. While metalation step proceeds leading stable Ar] species, ligand redistribution process complexes does not take place. Herein we report density functional theory study in combination electronic structure energy decomposition analyses shed light on steric requirements such complexes. Our findings show that formation depends right balance between intramolecular X⋅⋅⋅X Na⋅⋅⋅X (X=H, F, Cl, Br) interactions. latter further induces ‘seesaw effect’ , whereby aryl acts as ‘seesaw’ allowing two X atoms ortho positions interdependently interact Na. Only by considering both attractive repulsive Na(X)⋅⋅⋅X interactions, correct stability observed experiments can be predicted computationally. We envision these insights guide rational design metal for C−C coupling, field is still dominated scarce expensive precious metals.

Language: Английский

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Alkali‐Metal‐Alkoxide Powered Zincation of Fluoroarenes Employing Zinc Bis‐Amide Zn(TMP)₂

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 135(29)

Published: March 23, 2023

Abstract Reminiscent of Lochmann‐Schlosser superbase recipes, the addition two molar equivalents KO t Bu to Zn(TMP) 2 (TMP=2,2,6,6‐tetramethylpiperidide) transforms this mild zinc bis ‐amide base a powerful metalating agent able perform facile regioselective zincation wide range sensitive fluoroarenes. Structural authentication intermediates post Zn−H exchange demonstrates activation both TMP groups form higher order bis‐aryl potassium zincates, isolable as solids and further functionalized in electrophilic interception reactions. Studies assessing role reveal that first equivalent undergoes co‐complexation with , enabling kinetic amide groups; whereas second stabilizes metalated intermediate preventing ligand redistribution. Showcasing its power, bimetallic Bu/Zn(TMP) partnership, can effect toluene benzene at room temperature.

Language: Английский

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α‐Difluoroalkylation of Benzyl Amines with Trifluoromethylarenes

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 135(40)

Published: Aug. 19, 2023

Abstract An α‐difluoroalkylation of benzyl amines with trifluoromethylarenes is disclosed herein. This protocol characterized by its operational simplicity, excellent chemoselectivity and broad scope—even advanced synthetic intermediates—, thus offering a new entry point to medicinally‐relevant α‐difluoroalkylated from simple, yet readily accessible, precursors.

Language: Английский

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