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DOI: 10.1055/s-0031-1289900
Reactions of Nitroalkenes with Nitroalkanes or Sulfur Ylides Catalyzed by Amine-Thiourea Bifunctional Polymeric Organocatalysts
Publication History
Publication Date:
23 November 2011 (online)
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Abstract
Non-cross-linked and cross-linked bifunctional polystyrenes bearing both amine and thiourea groups have been synthesized and used as organocatalysts in reactions between nitroalkenes and nitroalkanes or sulfur ylides. Control experiments using monofunctional polymers with only either amine or thiourea groups attached indicated that both functional groups were essential for efficient catalysis of the reactions studied. The non-cross-linked polystyrene was soluble in typical organic solvents and was used as a homogeneous catalyst, while the cross-linked polystyrene was used as a heterogeneous catalyst.
Key words
polymer-supported organocatalyst - polystyrene - JandaJel - nitroalkanes - nitroalkenes - sulfur ylides
- Supporting Information for this article is available online:
- Supporting Information
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References and Notes
See Supporting Information for details.
22
General Procedure
for the Michael Addition Reactions of Nitroalkanes to Nitrostyrenes
Catalyzed by Polymer 9
Nitrostyrene 13a-i (1 mmol) and catalyst 9 (0.05
mmol) were dissolved in 12 (2.6 mL, 30
mmol). The mixture was stirred at r.t. for 20 h, and then the reaction
mixture was purified directly by column chromatography to afford
the desired product14a-i as a mixture of stereoisomers. The syn/anti ratio
was determined by ¹H NMR analysis of the crude product
mixture.
General Procedure for the Cycloaddition Reactions Catalyzed by Polymer 9 Nitrostyrene 13a,c,d,f-l (0.5 mmol) and 9 (0.05 mmol) were dissolved in CHCl3 (1 mL). Sulfur ylide 15a-c (0.6 mmol) in CHCl3 (1 mL) was then added dropwise to the mixture. After stirring at r.t. for 24 h, the reaction mixture was purified directly by column chromatography to afford the desired products 16a-l. The anti/syn ratio was determined by ¹H NMR analysis of the crude product mixture.
25
General Procedure
for the Michael Addition Reactions of Nitroalkanes to Nitrostyrenes
Catalyzed by Polymer 18
To nitrostyrene 13a-i (1
mmol) in 12 (2.6 mL, 30 mmol) was added
catalyst 18 (0.1 mmol). The mixture was
stirred at r.t. for 15 h. The polymer was then removed by filtration, washed
with THF, and the filtrate was concentrated in vacuo to remove the
excess nitropropane. The syn/anti ratio was determined by ¹H
NMR analysis.
General Procedure
for the Reuse of Polymer 18
To nitrostyrene 13a (3.0 mmol) in 12 (90
mmol) was added catalyst 18 (0.3 mmol).
Cycles 3-5 were performed on a 1.5 mmol scale and cycle
6 was performed on a 1.2 mmol scale. The mixture was stirred at
r.t. for 15 h, and then the polymer was then removed by filtration,
washed with THF, and dried. The filtrate was concentrated in vacuo
to remove the excess nitropropane. The syn/anti ratio was determined by ¹H
NMR analysis to be 85:15 in all cycles.