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Synlett 2016; 27(13): 1963-1968
DOI: 10.1055/s-0035-1562344
DOI: 10.1055/s-0035-1562344
letter
Benzylic Ammonium Ylide Mediated Epoxidations
Further Information
Publication History
Received: 31 March 2016
Accepted after revision: 22 May 2016
Publication Date:
15 June 2016 (online)
![](https://www.thieme-connect.de/media/synlett/201613/lookinside/thumbnails/st-2016-b0225-l_10-1055_s-0035-1562344-1.jpg)
Abstract
A high yielding synthesis of stilbene oxides using ammonium ylides has been developed. It turned out that the amine leaving group plays a crucial role as trimethylamine gives higher yields than DABCO or quinuclidine. The amine group also influences the diastereoselectivity, and detailed DFT calculations to understand the key parameters of these reactions have been carried out.
Supporting Information
- Supporting information for this article is available online at http://dx.doi.org/10.1055/s-0035-1562344.
- Supporting Information
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References and Notes
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- 20 General Epoxidation Procedure Ammonium salt 6 (1 equiv) was suspended in dry THF (0.05 M) and stirred at 40 °C. t-BuOK (4 equiv) was added, and the mixture was stirred vigorously. After 10 min, 2 equiv of aldehyde 2 were added, and the mixture was stirred for 3 h at 40 °C. The reaction was then quenched by addition of a half-saturated NaCl solution. After phase separation, the aqueous phase was extracted three times with CH2Cl2, and the combined organic phases were dried with Na2SO4 and evaporated to dryness. Purification by column chromatography (gradient of heptanes and EtOAc) gave the corresponding epoxides in the reported yields as a mixture of diastereomers. Compound 5a: Obtained in 93% (trans/cis = 66:34) on a 0.5 mmol scale as a white solid. Analytical data match those reported previously.5,21 Selected Data 1H NMR (300 MHz, δ, CDCl3, 298 K):trans isomer: 3.94 (s, 2 H), 7.36–7.49 (m, 5 H);cis isomer: 4.42 (s, 2 H), 7.18–7.28 (m, 5 H) ppm. ESI-HRMS: m/zcalcd for C14H12O: 197.0961 [M + H]+; found: 197.0961.
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For selected reviews, see:
For seminal work on sulfur ylides, see:
For examples highlighting the use of sulfur ylides in epoxidation reactions, see:
For ammonium ylide mediated cyclopropanations, see:
For benzylic ammonium ylide mediated epoxidations, see:
For cyano-stabilized ammonium ylide mediated epoxidations, see:
For amide-stabilized ammonium ylide mediated epoxidations, see:
For ammonium ylide mediated aziridinations, see:
For seminal studies, see: