Mechanism and Origins of Nucleophile‐Controlled Regioselectivity of Palladium‐Catalyzed Allylic C‐H Amination of 1,4‐Dienes: A Computational Study DOI
Mengyao Zhang, Shiyu Wang, Hongli Wu

et al.

Asian Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: July 23, 2024

Abstract Density functional theory calculations have been conducted to investigate the palladium‐catalyzed allylic C−H amination of 1,4‐dienes with commonly available amines. The computations indicate that reaction begins bond cleavage through concerted proton and two‐electron transfer process forge η 3 ‐allyl Pd(II) species. ensuing C−N formation was found be highly dependent on basicity nucleophile, enabling regioselectivity switch upon change nucleophile. With weakly basic aromatic amine, occurs hydrogen‐bonding enabled inner‐sphere nucleophilic attack pathway. distance between reacting carbon atom terminal is responsible for Z / E ‐selectivity. primarily due steric repulsion allyl group ligand. On other hand, outer‐sphere pathway favored more aliphatic cyclic amine. coordinating mode moiety play a crucial role in determining regioselectivity.

Language: Английский

Intermolecular Buchwald–Hartwig Reactions for Enantioselective Synthesis of Diverse Atropisomers: Rerouting the C–N Forming Mechanism to Substrate Oxygen-Assisted Reductive Elimination DOI
Wei Wang, Mingwei Jiang, Junwei Li

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(24), P. 16567 - 16580

Published: June 7, 2024

Axially chiral biaryls featuring a C–N axis are important functional molecules in diverse fields. The asymmetric Buchwald–Hartwig reaction represents powerful strategy for these targets. Previous studies, however, have been predominantly restricted to intramolecular atroposelective coupling, likely due the steric and entropic effects reductive elimination of Pd(II) species with sterically congested aryl nitrogen groups. We now report two intermolecular coupling systems bulky NH lactams halohydrocarbons enabled by rerouting mechanism one that accommodates challenging substrates. Both exhibited group tolerance, excellent enantioselectivity, high Z selectivity (if applicable), affording atropisomeric biaryl olefins through de novo construction axis. Experimental computational studies were performed elucidate mechanism, switch pathways is traced effect (ortho substituent) halide substrate. A 2,6-disubstituted reorients proximal lactamide ligand its unusual O-ligation mode. With amide oxygen participation, this intermediate undergoes an accessible barrier five-membered ring transition state, pathway as well induction mode has much underexplored catalysis.

Language: Английский

Citations

6
Computational insights into the synergistic interplay of ligand and fluorine effects in palladium-catalyzed regiodivergent decarboxylative allylic alkylation DOI
Shiyu Wang, Hongli Wu, Xiangyang Tang

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(10), P. 2870 - 2883

Published: Jan. 1, 2024

DFT calculations were performed to investigate palladium-catalyzed decarboxylative allylic alkylation of allyl difluoro-β-ketoesters. The synergistic effects ligand and fluorine substituents on regioselectivity uncovered.

Language: Английский

Citations

4
Cobalt‐Catalyzed Allylic Alkylation at sp3‐Carbon Centers DOI
Ebbin Joseph, Jon A. Tunge

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(47)

Published: June 13, 2024

Abstract The rising demand and financial costs of noble transition metal catalysts have emphasized the need for sustainable catalytic approaches. Over past few years, base‐metal emerged as ideal candidates to replace their noble‐metal counterparts because abundance easiness handling. Despite significant advancements achieved with precious metals, earth‐abundant cobalt efficient alternatives allylic substitution reactions. In this review, alkylations at sp 3 ‐carbon centers mediated by will be discussed, a special focus on mechanistic features, scope, limitations.

Language: Английский

Citations

1
Reductive coupling of allenyl/allyl carbonate with alkyne under dual cobalt-photoredox catalysis DOI Creative Commons

Subhankar Pradhan,

Dhananjay Satav,

Sayan Dutta

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Nov. 29, 2024

Language: Английский

Citations

1
Effect of ligand coordination on the mechanism and regioselectivity of cobalt-catalyzed hydroboration/cyclization of 1,6-enynes DOI

Yu-Fei Fu,

Xiaojun Liu, Dezhan Chen

et al.

Journal of Catalysis, Journal Year: 2023, Volume and Issue: 428, P. 115190 - 115190

Published: Nov. 1, 2023

Language: Английский

Citations

2
A Precise Route to Tetrasubstituted Allyl Amines via Regioselective Dicarbofunctionalization of Masked Propargyl Amines DOI
Aradhana Sahoo, Shubham Dutta, Akhila K. Sahoo

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(45), P. 9746 - 9751

Published: Nov. 7, 2024

Allyl amines are vital components in various biologically important molecules and play a significant role their function. Presently, most methods geared toward the preparation of di- trisubstituted allyl amines, leaving gap for development more versatile approaches. We herein describe an approach to yield tetrasubstituted through palladium (Pd)-catalyzed regioselective dicarbofunctionalization masked N-phthalimide-protected propargyl amines. The cationic Pd-intermediate conjunction with amine exerts collective control reaction regioselectivity. This method accommodates wide range alkynes, aryl boronic acids, diazonium salts offering direct access unusual

Language: Английский

Citations

0
Mechanism and Origins of Nucleophile‐Controlled Regioselectivity of Palladium‐Catalyzed Allylic C‐H Amination of 1,4‐Dienes: A Computational Study DOI
Mengyao Zhang, Shiyu Wang, Hongli Wu

et al.

Asian Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: July 23, 2024

Abstract Density functional theory calculations have been conducted to investigate the palladium‐catalyzed allylic C−H amination of 1,4‐dienes with commonly available amines. The computations indicate that reaction begins bond cleavage through concerted proton and two‐electron transfer process forge η 3 ‐allyl Pd(II) species. ensuing C−N formation was found be highly dependent on basicity nucleophile, enabling regioselectivity switch upon change nucleophile. With weakly basic aromatic amine, occurs hydrogen‐bonding enabled inner‐sphere nucleophilic attack pathway. distance between reacting carbon atom terminal is responsible for Z / E ‐selectivity. primarily due steric repulsion allyl group ligand. On other hand, outer‐sphere pathway favored more aliphatic cyclic amine. coordinating mode moiety play a crucial role in determining regioselectivity.

Language: Английский

Citations

0