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Synlett 2015; 26(12): 1737-1743
DOI: 10.1055/s-0034-1380810
DOI: 10.1055/s-0034-1380810
letter
Polyethyleneimine-Supported Triphenylphosphine and Its Use as a Highly Loaded Bifunctional Polymeric Reagent in Chromatography-Free One-Pot Wittig Reactions
Further Information
Publication History
Received: 25 March 2015
Accepted after revision: 20 April 2015
Publication Date:
18 June 2015 (online)
![](https://www.thieme-connect.de/media/synlett/201512/lookinside/thumbnails/st-2015-w0209-l_10-1055_s-0034-1380810-1.jpg)
Abstract
A polyethyleneimine-supported triphenylphosphine reagent has been synthesized and used as a highly loaded bifunctional homogeneous reagent in a range of one-pot Wittig reactions that afforded high yields of the desired products after simple purification procedures. The approach also served efficiently in tandem reaction sequences involving a one-pot Wittig reaction followed by conjugate reduction of the newly formed alkene product in situ. In these transformations, the phosphine oxide groups generated in the Wittig reaction served as the catalyst for activating trichlorosilane in the subsequent reduction reaction.
Key words
conjugate reduction - polyethyleneimine - polymer supported reagents - triphenylphosphine - Wittig reactionsSupporting Information
- Supporting information for this article is available online at http://dx.doi.org/10.1055/s-0034-1380810.
- Supporting Information
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References and Notes
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- 24 General Procedure for Tandem Wittig/Conjugate Reduction Reactions: The Wittig reaction was conducted as before,[20] but when it was determined to be complete, the mixture was cooled to 0 °C in an ice-water bath, and HSiCl3 (0.4 mmol) was added. The reaction mixture was stirred for 2 h at 0 °C and then warmed to room temperature. When the reaction was determined to be complete by TLC analysis, the excess HSiCl3 and solvent were evaporated under reduced pressure. The resulting mixture was dissolved in CHCl3 (20 mL) and then added to sat. aq Na2CO3 (20 mL). The mixture was stirred for 30 min, then the aqueous phase was separated and washed with CH2Cl2 (3 × 15 mL). The combined organic layer was dried over MgSO4 and concentrated under reduced pressure to afford the desired product in an essentially pure state based on 1H NMR analysis. 1-(4-Bromophenyl)-3-phenylpropan-1-one (21Ad): 1H NMR (400 MHz, CDCl3): δ = 7.82 (d, J = 8.6 Hz, 2 H), 7.59 (d, J = 8.6 Hz, 2 H), 7.30–7.21 (m, 5 H), 3.26 (t, J = 7.5 Hz, 2 H), 3.06 (t, J = 7.5 Hz, 2 H). 13C NMR (100 MHz, CDCl3): δ = 198.3, 141.1, 135.6, 132.0, 129.6, 128.7, 128.5, 128.3, 126.3, 40.5, 30.1. MS: m/z calcd for C15H13BrO: 288.0; found 288.2.
For selected recent reviews regarding the Wittig reaction, see:
For reviews of polymer-supported phosphines and their uses, see:
For examples of the use of ion-supported phosphines in Wittig reactions, see:
For recent examples of our research regarding polymer-supported reagents and catalysts, see:
For similar reactions studied by others and the inspiration for our research in this area, see: