A Recyclable Palladium-Catalyzed Synthesis of 2-Methylene-2,3-Dihydrobenzofuran-3-ols by Cycloisomerization of 2-(1-Hydroxyprop-2-ynyl)phenols in Ionic Liquids
Abstract
:1. Introduction
2. Results and Discussion
Entry | Ionic Liquid | T (°C) | Conversion of 1a b (%) | Yield of 2a c (%) |
---|---|---|---|---|
1 | BmimBF4 | 70 | 80 | 60 |
2 d | BmimBF4 | 70 | 100 | 82 |
3 | BmimBF4 | 100 | 100 | 86 |
4 e | BmimBF4 | 100 | 100 | 80 |
5 f | BmimBF4 | 100 | 100 | 63 |
6 g | BmimBF4 | 100 | 100 | 65 |
7 | BmimCl | 100 | 100 | 51 |
8 | BmimPF6 | 100 | 100 | 58 |
9 | BmimN(CN)2 | 100 | 100 | 63 |
10 | BmimOTf | 100 | 60 | 23 |
Entry | 1 | 2 | Yield of 2 (%) b | ||||||
---|---|---|---|---|---|---|---|---|---|
Run 1 c | Run 2 c | Run 3 c | Run 4 c | Run 5 c | Run 6 c | Run 7 c | |||
1 | | | 86 | 85 | 87 | 86 | 85 | 86 | 87 |
2 | | | 84 | 86 | 82 | 75 | 72 | 73 | 72 |
3 | | | 70 | 71 | 71 | 68 | 70 | 69 | 70 |
4 | | | 78 | 80 | 78 | 80 | 81 | 81 | 80 |
5 | | | 80 | 81 | 79 | 80 | 78 | 81 | 79 |
6 | | | 75 | 77 | 76 | 77 | 75 | 76 | 78 |
7 | | | 76 | 76 | 77 | 75 | 78 | 74 | 77 |
Entry | 1 | R | t (h) | 3 or 4 | Yield of 3 or 4 b (%) |
---|---|---|---|---|---|
1 | | H | 3 | | 65 |
2 | | H | 3 | | 55 |
3 | | H | 3 | | 54 |
4 | | H | 3 | | 71 |
5 | | H | 3 | | 56 |
6 | | H | 3 | | 52 |
7 | | H | 3 | | 54 |
8 | 1a | Me | 18 | | 80 |
9 | 1b | Me | 18 | | 65 |
10 | 1c | Me | 18 | | 52 |
11 | 1d | Me | 15 | | 70 |
12 | 1e | Me | 18 | | 52 |
13 | 1f | Me | 18 | | 55 |
14 | 1g | Me | 18 | | 60 |
3. Experimental
3.1. General
3.2. Preparation of Substrates
3.3. Preparation of Ionic Liquids
3.4. General Procedure for the PdI2/KI-Catalyzed Cycloisomerization of 2-(1-Hydroxyprop-2-ynyl)phenols 1 to Give 2-Methylene-2,3-Dihydrobenzofuran-3-ols 2
3.5. General Procedure for the One-Pot Synthesis of 2-Hydroxymethylbenzofurans 3 and 2-Methoxy- methylbenzofurans 4 Starting From 2-(1-Hydroxyprop-2-ynyl)phenols 1
3.6. Characterization of Products
4. Conclusions
Acknowledgments
Conflicts of Interest
References
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Mancuso, R.; Gabriele, B. A Recyclable Palladium-Catalyzed Synthesis of 2-Methylene-2,3-Dihydrobenzofuran-3-ols by Cycloisomerization of 2-(1-Hydroxyprop-2-ynyl)phenols in Ionic Liquids. Molecules 2013, 18, 10901-10911. https://doi.org/10.3390/molecules180910901
Mancuso R, Gabriele B. A Recyclable Palladium-Catalyzed Synthesis of 2-Methylene-2,3-Dihydrobenzofuran-3-ols by Cycloisomerization of 2-(1-Hydroxyprop-2-ynyl)phenols in Ionic Liquids. Molecules. 2013; 18(9):10901-10911. https://doi.org/10.3390/molecules180910901
Chicago/Turabian StyleMancuso, Raffaella, and Bartolo Gabriele. 2013. "A Recyclable Palladium-Catalyzed Synthesis of 2-Methylene-2,3-Dihydrobenzofuran-3-ols by Cycloisomerization of 2-(1-Hydroxyprop-2-ynyl)phenols in Ionic Liquids" Molecules 18, no. 9: 10901-10911. https://doi.org/10.3390/molecules180910901