- On the relative migratory aptitudes of carbon and heteroatoms in borate complexes. A surprising α-thia effect
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Dimethylsulfoxonium methylide reacts with dicyclohexyl(α- thiophenylmethyl)methylborane via 1,2-alkyl migration and alkyldithiaborolane via 1,2-sulfur migration.
- Stoddard, Jonathan M.,Shea, Kenneth J.
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p. 830 - 831
(2007/10/03)
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- Preparative Aspects of 1,3-Dithiolanes Synthesizable from β-Dicarbonyl Compounds
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The reaction of 1,2-ethanedithiol (1) with the β-dicarbonyl compounds 2 leads to the 1,3-dithiolanes 3 which are accessible to regioselective reactions at the free carbonyl function.Thus the derivatives of the β-keto acid esters can be hydrolyzed to give the corresponding carboxylic acids 4 which make the ester group modified 1,3-dithiolanes 3 accessible in good yields.Addition of trimethyloxonium tetrafluoroborate produces the monodithiolanium salts 6 which on hydrolysis rapidly decompose into 2 and the vinyl thioethers 8.Reaction of 3 with Grignard reagents 10 yields the 2-(2-hydroxyalkyl)-1,3-dithiolanes 11.Dethioacetalization of 11 with HgO/BF3 leads to the β-hydroxy ketones 12.The retro reaction of 3 leads to the basic compounds 2 which, however, are obtained only in moderate yields. - Finally the performance of the sensitive silylenol ether 13 starting from 3g is described.
- Stahl, Ingfried,Schramm, Berthold,Manske, Rainer,Gosselck, Juergen
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p. 1158 - 1172
(2007/10/02)
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