10.1002/ejoc.201900478
European Journal of Organic Chemistry
COMMUNICATION
A
and Me2S.[11r,s] Later, the corresponding
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the aldehyde
aldehydes A will react with NH2OH to generate aldoxime
intermediates B after dehydration. Then the aldoxime B will
further react with SO2F2 to provide the corresponding sulfonyl
ester C. Subsequently, the sulfonyl ester C will proceed a beta-
elimination to generate the desired nitrile 2.
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Conclusions
In summary,
a new transition-metal-free one-pot cascade
process has been developed which allowed transformation of a
broad range of inexpensive, easily accessible, and abundant
alcohols into nitriles without introducing an “additional carbon
atom”. The reported reaction proceeded with the feathers of mild
condition, high efficiency, wide scope and excellent functional-
group compatibility. Moreover, the formal synthesis of important
drugs was also achieved using this method. We anticipate that
this easy, mild and practical method will have wide applications.
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Experimental Section
1. General procedure
Alcohol (2.0 mmol, 1.0 eq.), K2CO3 (331.2 mg, 2.4 mmol, 1.2 eq.), and
DMSO (15.0 mL) were added to an oven-dried reaction tube (50 mL) that
was equipped with a stirrer bar. The tube was fitted with a plastic stopper
and SO2F2 gas was introduced into the stirring reaction mixture by
bubbling from an SO2F2 balloon at room temperature for 12 h. After the
alcohol was completely consumed (by TLC), NH2OH.HCl (152.9 mg, 2.2
mmol, 1.1 eq.), K2CO3 (151.8 mg, 1.1mmol, 0.55 eq.) were added into
the reaction mixture, and reacted at room temperature for 30-60 min. The
reaction was monitored by TLC. After the aldehyde was completely
consumed, another portion of the K2CO3 (1.38 g, 10 mmol) was added
and the reaction tube was covered with a plastic stopper before the
SO2F2 gas was introduced into the stirring reaction mixture by slow
bubbling through a SO2F2 balloon at the room temperature for an
additional 12 h. After completion of the reaction, the resulting reaction
mixture was diluted with water and extracted with EtOAc (3×20 mL) and
the combined organic layer was washed with brine, dried over anhydrous
Na2SO4, and concentrated to dryness. The residue was purified by
column chromatography on silica gel to afford the desired nitriles.
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Acknowledgments
We are grateful to the National Natural Science Foundation of
China (Grant No. 21772150), the Wuhan Applied Fundamental
Research Program of Wuhan Science and Technology Bureau
(grant NO. 2017060201010216) and Wuhan University of
Technology for their financial support.
Keywords: transition-metal-free; one-pot; alcohols; nitriles;
sulfuryl fluoride
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