Direct Base-Assisted C‒H Cyclonickelation of 6-Phenyl-2,2′-bipyridine
Abstract
:1. Introduction
2. Results
3. Discussion
4. Materials and Methods
4.1. Materials
4.2. Cyclonickelation Experiments
5. Conclusions
Supplementary Materials
Author Contributions
Funding
Acknowledgments
Conflicts of Interest
References
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Sample Availability: Samples of the compounds [Ni(Phbpy)Br], [Ni(HPhbpy)Br2]2, and [Ni(Phbpy)(OAc)] are available from the authors. |
a | NiX2 | Base (eq.) | Solvent | Time (h) | T (°C) | Yield (%) | Analysis | |
---|---|---|---|---|---|---|---|---|
1 | A | NiBr2 | no base | toluene | 60 | 111 g | 0 | visual b |
2 | A | NiBr2 | NEt3 (11.5) | toluene | 48 | 111 g | 1.5 | 1H NMR c |
3 | A | NiBr2 | NaHCO3 (2) | toluene/MeOH | 3 | 111 g | 2.5 | 1H NMR |
4 | A | NiBr2 | Na2CO3 (4) | solid | 1 | 170 | 0 | visual b |
5 | B | NiBr2 | Cs2CO3 (2) | toluene | 66 | 111 g | trace | 1H NMR |
6 | B | NiBr2 | Na2CO3 (3) | toluene | 90 | 111 g | 19 | 1H NMR |
7 | C | [Ni(HPhbpy)Br2] | NaOtBu (2) | diethyl ether | 16 | 23 | 0 | 1H NMR |
8 | C | [Ni(HPhbpy)Br2] | KOAc/K2CO3 (2/4) | toluene | 16 | 111 g | 6 | 1H NMR |
9 | C | [Ni(HPhbpy)Br2] | KOAc/K2CO3 (2/4) | toluene | 62 | 111 g | 28 | 1H NMR |
10 | A | Ni(OAc)2.4H2O | - | toluene/EtOH//DME | 15 | 111 | 5 d | XRD |
11 | A | Ni(OAc)2 | - | solid | 1 | 250 | 0 e | visual b |
12 | A | Ni(OAc)2 | - | solid | 1 | 180 | 4 f | XRD |
Entry | Solvent | Time (h) | Tbat (°C) | Tb.p. (°C) | Yield (%) | |
---|---|---|---|---|---|---|
13 | toluene | 72 | 120 | 111 | 0.099 | 43 |
14 | chlorobenzene | 64 | 160 | 131 | 0.188 | 91 |
15 | 1,2-dichlorobenzene | 25 | 190 | 180 | 0.225 | 98 |
16 | p-xylene | 25 | 160 | 138 | 0.074 | 100 |
17 | benzonitrile | 20 | 200 | 190 | 0.333 | 0 |
18 | p-xylene c (from NiBr2) | 64 | 160 | 138 | 0.074 | 93 |
19 | 1,2-dichlorobenzene d (no base) | 64 | 190 | 180 | 0.225 | 15 |
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Vogt, N.; Sivchik, V.; Sandleben, A.; Hörner, G.; Klein, A. Direct Base-Assisted C‒H Cyclonickelation of 6-Phenyl-2,2′-bipyridine. Molecules 2020, 25, 997. https://doi.org/10.3390/molecules25040997
Vogt N, Sivchik V, Sandleben A, Hörner G, Klein A. Direct Base-Assisted C‒H Cyclonickelation of 6-Phenyl-2,2′-bipyridine. Molecules. 2020; 25(4):997. https://doi.org/10.3390/molecules25040997
Chicago/Turabian StyleVogt, Nicolas, Vasily Sivchik, Aaron Sandleben, Gerald Hörner, and Axel Klein. 2020. "Direct Base-Assisted C‒H Cyclonickelation of 6-Phenyl-2,2′-bipyridine" Molecules 25, no. 4: 997. https://doi.org/10.3390/molecules25040997