Improved, Odorless Access to Benzo[1,2-d;4,5-d′]- bis[1,3]dithioles and Tert-butyl Arylsulfides via C-S Cross Coupling
Abstract
:1. Introduction
2. Results and Discussion
3. Experimental
3.1. General
3.2. Synthetic Procedures
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Conflicts of Interest
References
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Sample Availability: Samples of the compounds are not available from the authors. |
No. | T [°C] | Ligand | Conversion * [%] | 7 * [%] | 8 * [%] | Selectivity to 7 [%] |
---|---|---|---|---|---|---|
1 | 50 | Ph3P | 23 | 14 | 9 | 59 |
2 | 50 | XPhos | 7 | 0 | 7 | 0 |
3 | 50 | XantPhos | 0 | 0 | 0 | 0 |
4 | 80 | Ph3P | 100 | 100 | 0 | 100 |
5 | 80 | dppf | 69 | 34 | 35 | 49 |
6 | 80 | XantPhos | 38 | 2 | 36 | 4.8 |
7 | 80 | XPhos | 43 | 0 | 43 | 0 |
8 | 80 | BrettPhos | 45 | 0 | 45 | 0 |
9 | 80 | SPhos | 62 | 0 | 62 | 0 |
10 | 80 | nBu3P | 78 | 61 | 17 | 78 |
11 | 80 | none | 59 | 0 | 59 | 0 |
12 ** | 80 | none | 72 | 0 | 72 | 0 |
13 ** | 80 | SPhos | 65 | 0 | 65 | 0 |
No. | Base | Solvent | Conversion * [%] | 7 * [%] | 8 * [%] | Selectivity to 7 [%] |
---|---|---|---|---|---|---|
1 | KOtBu | DMF | 100 | 100 | 0 | 100 |
2 | KOtBu | nBuOH | 61 | 61 | 0 | 100 |
3 | Cs2CO3 | DMF | 19 | 19 | 0 | 100 |
4 | K2CO3 | DMF | 42 | 42 | 0 | 100 |
5 ** | K2CO3 | DMF | 0 | 0 | 0 | 0 |
6 | K3PO4 | DMF | 43 | 43 | 0 | 100 |
7 ** | K3PO4 | DMF | 12 | 12 | 0 | 100 |
8 | KOtBu *** | DMF | 22 | 22 | 0 | 100 |
No. | Substrate | Catalyst | T [°C] | Yield * [%] |
---|---|---|---|---|
1 * | 1,4-diiodobenzene | Ph3P/Pd2dba3 | 80 | 100 |
2 * | 1,4-diiodobenzene | Ph3P/Pd2dba3 | 50 | 100 |
3 | 4-nitrobromobenzene | Ph3P/Pd2dba3 | 25 | 100 |
4 | 4-nitrobromobenzene | none | 25 | 100 |
5 ** | 4-chloroansiole | Ph3P/Pd2dba3 | 80 | 0 |
6 ** | 4-chloroanisole | none | 80 | 0 |
7 ** | 4-fluoroanisole | Ph3P/Pd2dba3 | 80 | 0 |
8 ** | 4-fluoroanisole | none | 80 | 0 |
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Kopp, K.; Schiemann, O.; Fleck, N. Improved, Odorless Access to Benzo[1,2-d;4,5-d′]- bis[1,3]dithioles and Tert-butyl Arylsulfides via C-S Cross Coupling. Molecules 2020, 25, 3666. https://doi.org/10.3390/molecules25163666
Kopp K, Schiemann O, Fleck N. Improved, Odorless Access to Benzo[1,2-d;4,5-d′]- bis[1,3]dithioles and Tert-butyl Arylsulfides via C-S Cross Coupling. Molecules. 2020; 25(16):3666. https://doi.org/10.3390/molecules25163666
Chicago/Turabian StyleKopp, Kevin, Olav Schiemann, and Nico Fleck. 2020. "Improved, Odorless Access to Benzo[1,2-d;4,5-d′]- bis[1,3]dithioles and Tert-butyl Arylsulfides via C-S Cross Coupling" Molecules 25, no. 16: 3666. https://doi.org/10.3390/molecules25163666