Development of Fluorous Lewis Acid-Catalyzed Reactions
Abstract
:Contents
- Introduction
- Fluorous Lewis Acid Catalysts
- Fluorous Biphasic Catalysis by Fluorous Lewis Acids
- Fluorous Biphasic Reactions Containing Water
- Continuous-flow Reaction in FBS
- Fluorous Silica Gel-Supported Lewis Acid Catalysts
- Supercritical Carbon Dioxide as a Reaction Medium
- Conclusions
Introduction
Fluorous Lewis Acid Catalysts
Fluorous Biphasic Catalysis by Fluorous Lewis Acids
% yieldb,c | ||
cyclea | Yb[C(SO2-n-C8F17)3]3 | Sc[C(SO2-n-C8F17)3]3 |
1 | 99 | 99 (98) |
2 | 99 (96) | 100 (98) |
3 | 98 | 99 |
4 | 99 | 99 |
5 | 99 (96) | 100 (98) |
catalyst | % yielda | ratio (p / o)a |
Hf[N(SO2-n-C8F17)2]4 | 80 | 100 : 0 |
Hf[N(SO2-n-C8F17)2]4b | 92 | >99 : <1 |
Hf(OTf)4 | 49 | 97 : 3 |
Sc(OTf)3 | 45 | 98 : 2 |
Yb(OTf)3 | 16 | 97 : 3 |
AlCl3c | 2 | 100 : 0 |
Fluorous Biphasic Reactions Containing Water
R1CO2H | R2OH | conditions | % yielda | % selectivityb |
AcOH | c-C6H11OH | 50 °C, 8 h | 82 | 98 |
c-C6H11CO2H | n-C4H9OH | 70 °C, 15 h | 92 | 97 |
c-C6H11CO2H | PhCH2OH | 50 °C, 24 h | 89 | 98 |
c-C6H11CO2H | c-C6H11OH | 50 °C, 24 h | 55 | 98 |
PhCO2H | n-C4H9OH | 90 °C, 15 hc | 85 | 96 |
CH2=CH(CH3)CO2H | CH3OHd | 60 °C, 8 h | 86 | 98 |
catalyst | cyclea | % yieldb,c | % selectivityd |
Sn[N(SO2-n-C8F17)2]4 | 1 | 93 (91) | 99 |
4 | 93 | 99 | |
Sn[N(SO2-n-C8F17)2]4e | 1 | 68 | 80 |
Sn[N(SO2-n-C8F17)2]2 | 1 | 48 | 83 |
Sn(OTf)2 | 1 | 37 | 87 |
Hf[N(SO2-n-C8F17)2]4 | 1 | 82 | 92 |
Hf(OTf)4 | 1 | 41 | 91 |
Sc[N(SO2-n-C8F17)2]3 | 1 | 53 | 69 |
Sc(OTf)3 | 1 | 31 | 66 |
Continuous-flow Reaction in FBS
Fluorous Silica Gel-Supported Lewis Acid Catalysts
catalyst | cyclea | % yieldb,c | % selectivityc,d |
fluorous SiO2-Sn[N(SO2-n-C8F17)2]4 | 1 | 79 (87) | 100 (89) |
2 | 75 (89) | 97 (92) | |
3 | 73 (86) | 96 (90) | |
4 | 71 (88) | 91 (93) | |
ODS SiO2-Sn[N(SO2-n-C8F17)2]4 | 1 | 60 | 88 |
2 | 41 | 84 | |
3 | 28 | 82 | |
SiO2-Sn[N(SO2-n-C8F17)2]4 | 1 | 43 | 93 |
2 | 34 | 100 | |
3 | 24 | 86 |
Supercritical Carbon Dioxide as a Reaction Medium
(a) Supercritical carbon dioxide/fluorous solvent system
cyclea | % yieldb,c |
1 | 99 (98) |
2 | 99 |
3 | 99 |
4 | 99 |
5 | 99 |
(b) Supercritical carbon dioxide system
% yieldb,c | ||
cyclea | Yb[N(SO2-n-C8F17)2]3 | Sc[C(SO2-n-C8F17)3]3 |
1 | 99 (98) | 99 (98) |
2 | 99 | 100 (98) |
3 | 98 | 99 |
% yieldb,c | ||
cyclea | Yb[N(SO2-n-C8F17)2]3 | Sc[C(SO2-n-C8F17)3]3 |
1 | 79 (77) | 82 (79) |
2 | 77 | 80 |
3 | 77 | 79 |
Conclusions
Acknowledgements
References and Notes
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Yoshida, A.; Hao, X.; Yamazaki, O.; Nishikido, J. Development of Fluorous Lewis Acid-Catalyzed Reactions. Molecules 2006, 11, 627-640. https://doi.org/10.3390/11080627
Yoshida A, Hao X, Yamazaki O, Nishikido J. Development of Fluorous Lewis Acid-Catalyzed Reactions. Molecules. 2006; 11(8):627-640. https://doi.org/10.3390/11080627
Chicago/Turabian StyleYoshida, Akihiro, Xiuhua Hao, Osamu Yamazaki, and Joji Nishikido. 2006. "Development of Fluorous Lewis Acid-Catalyzed Reactions" Molecules 11, no. 8: 627-640. https://doi.org/10.3390/11080627