Iron-Catalyzed Cross-Coupling of Bis-(aryl)manganese Nucleophiles with Alkenyl Halides: Optimization and Mechanistic Investigations
Abstract
:1. Introduction
2. Results
3. Discussion
4. Materials and Methods
4.1. Materials and Instruments
4.2. Chemicals, Solvents, and Typical Procedures
4.2.1. Typical Procedure for the One-Pot Preparation of Bis-(aryl)manganese Reagents 1a–g
4.2.2. Typical Procedure for the Cross-Coupling Reactions of Bis-(aryl)manganese Reagents 1a–g with Different Electrophiles 3a–e
4.3. Studies on the Catalytically Active Species and Catalytic Cycle
5. Conclusions
Supplementary Materials
Author Contributions
Funding
Acknowledgments
Conflicts of Interest
References and Notes
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Sample Availability: Samples of all the compounds described in this article are available from the authors. |
Entry | Catalyst (10 mol%) | Yield (%) a |
---|---|---|
1 | none | 60 b |
2 | FeBr2 | 42 |
3 | FeCl3 | 54 |
4 | FeBr3 | 57 |
5 | FeCl2 | 64 |
6 | Fe(acac)2 | 67 |
7 | Fe(acac)3 (>99% purity) | 79 |
Entry | Ar2Mn | Electrophile | Yield (%) b | Entry | Ar2Mn | Electrophile | Yield (%) b |
---|---|---|---|---|---|---|---|
1 | 1a | 3b: Z/E = 10:90 | 4b: 98, Z/E = 1:99 (24, Z/E = 20:80) c | 8 | 1e | 3a | 4i: 64, Z/E = 1:99 (51, Z/E = 57:43) c |
2 | 1b | 3a | 4c: 69, Z/E = 1:99 (58, Z/E = 69:31) c | 9 | 1f | 3b: Z/E = 10:90 | 4j: 78, Z/E = 1:99 (39, Z/E = 20:80) c |
3 | 1c | 3b: Z/E = 10:90 | 4d: 80, Z/E = 1:99 (8, Z/E = 1:99) c | 10 | 1f | 3a | 4k: 84, Z/E = 1:99 (48, Z/E = 99:1) c |
4 | 1c | 3a | 4e: 57, Z/E = 1:99 (66, Z/E = 72:28) c | 11 | 1g | 3b: Z/E = 10:90 | 4l: d 20, Z/E = 21:79 91, Z/E = 5:95 e (traces, Z/E = 50:50) c |
5 | 1c | 3c: Z/E = 18:82 | 4f: 82, Z/E = 1:99 (80, Z/E = 53:47) c | 12 | 1d | 3e: Z/E = 98:2 | 4m: 74, Z/E = 98:2 (19, Z/E = 73:27) c |
6 | 1c | 3d | 4g: 87, Z/E = 9:91 (77, Z/E = 4:96) c | 13 | 1e | 3e: Z/E = 98:2 | 4n: 66, Z/E = 70:30 (41, Z/E = 72:28)c |
7 | 1d | 3a | 4h: 77, Z/E = 1:99 (74, Z/E = 81:19) c |
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Rousseau, L.; Desaintjean, A.; Knochel, P.; Lefèvre, G. Iron-Catalyzed Cross-Coupling of Bis-(aryl)manganese Nucleophiles with Alkenyl Halides: Optimization and Mechanistic Investigations. Molecules 2020, 25, 723. https://doi.org/10.3390/molecules25030723
Rousseau L, Desaintjean A, Knochel P, Lefèvre G. Iron-Catalyzed Cross-Coupling of Bis-(aryl)manganese Nucleophiles with Alkenyl Halides: Optimization and Mechanistic Investigations. Molecules. 2020; 25(3):723. https://doi.org/10.3390/molecules25030723
Chicago/Turabian StyleRousseau, Lidie, Alexandre Desaintjean, Paul Knochel, and Guillaume Lefèvre. 2020. "Iron-Catalyzed Cross-Coupling of Bis-(aryl)manganese Nucleophiles with Alkenyl Halides: Optimization and Mechanistic Investigations" Molecules 25, no. 3: 723. https://doi.org/10.3390/molecules25030723