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Synlett 2018; 29(13): 1791-1795
DOI: 10.1055/s-0037-1610194
DOI: 10.1055/s-0037-1610194
letter
Reaction of 1-Trimethylsilyl-1,2-epoxy-3-alkanols with Alkynes and Application to the Synthesis of 18-HEPE
This work was supported by JSPS KAKENHI Grant Number JP15H05904.Further Information
Publication History
Received: 27 April 2018
Accepted after revision: 04 June 2018
Publication Date:
29 June 2018 (online)
![](https://www.thieme-connect.de/media/synlett/201813/lookinside/thumbnails/st-2018-u0263-l_10-1055_s-0037-1610194-1.jpg)
Abstract
A reaction of epoxy alcohols (anti and/or syn isomers) derived from (E)-TMS-CH=CHCH(OH)R with TMS-C≡CLi in THF/HMPA stereoselectively afforded (E)-TMS-C≡C-CH=CHCH(OH)R. The (E) stereochemistry was independent of the anti/syn stereochemistry, but the syn isomers showed higher reactivity than the anti isomers. The reaction was applied to the synthesis of (18R)- and (18S)-HEPE.
Key words
alkynes - epoxide ring opening - silicon - stereoselective synthesis - Castro–Stephens coupling - eicosapentaenoic acidSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0037-1610194.
- Supporting Information
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References and Notes
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- 15 Castro–Stephens coupling of rac-7 (1.2 equiv) with Z-allylic bromide i (1 equiv) using CuI (2 equiv), NaI (2 equiv), and K2CO3 (1.5 equiv) at rt in DMF gave a mixture of rac-12 and the regioisomer ii in a 3:1 ratio (1H NMR), which were hardly separated by chromatography on silica gel (Scheme 6). The mixture was converted into 18-HEPE and the regioisomer by a sequence of reactions: 1) TBAF; 2) Zn (Cu/Ag); 3) LiOH; an attempted separation at each step was hardly successful.
Previous syntheses of 18-HEPE: