Synthesis of S,S,O-orthoesters and 1,1-difluoroalkyl ethers via reaction of peroxides with lithiated 1,3-dithianes

Organic Letters

Volumn 16, Issue 20, 2014, Pages 5235-5237

  Kyasa, ShivaKumar ^a   Dussault, Patrick H ^a  

^a UNIVERSITY OF NEBRASKA LINCOLN   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

1,3-DITHIANE; ETHER DERIVATIVE; HETEROCYCLIC COMPOUND; PEROXIDE; PYRIDINE; PYRIDINE DERIVATIVE;

CHEMICAL STRUCTURE; CHEMISTRY; SYNTHESIS;

ETHERS; HETEROCYCLIC COMPOUNDS; MOLECULAR STRUCTURE; PEROXIDES; PYRIDINES;

EID: 84908056848     PISSN: 15237060     EISSN: 15237052     Source Type: Journal    
DOI: 10.1021/ol502726p     Document Type: Article

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29. General procedure for synthesis of S,S,O-orthoesters: n-BuLi (0.75 mmol) was added to a solution of the dithiane (0.5 mmol) in dry THF (4 mL) at room temperature. The reaction was stirred for 10 min, and then the peroxide (0.5 mmol) was added dropwise as a solution in THF (1 mL/mmol scale) via syringe. The reaction was stirred for 40 min and then quenched by addition of acetone (0.5 mL/mmol substrate). The resulting solution was filtered through a 2-in. pad of neutral alumina (50-200 μm) and flushed with 25 mL of ethyl acetate. The residue obtained upon concentration of the filtrate was purified by silica gel chromatography. For reactions using only 1 equiv of n-BuLi, compounds 5b, 5,d and 5e were additionally purified by preparative HPLC using 5% ethyl acetate/hexanes. For reactions on a 5 mmol scale, the crude reaction mixture was diluted with 120 mL of hexanes and washed with water (2 x 20 mL). The separated organic layer was dried over sodium sulfate and the concentrated residue purified by chromatography (1% ethyl acetate/hexanes).
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