Discovery of practical production processes for arylsulfur pentafluorides and their higher homologues, bis- and tris(sulfur pentafluorides): Beginning of a new era of “super-trifluoromethyl” arene chemistry and its industry

• Teruo Umemoto,
• Lloyd M. Garrick and
• Norimichi Saito

Beilstein J. Org. Chem. 2012, 8, 461–471, doi:10.3762/bjoc.8.53

• to be thermal isomerization of trans-2a to cis-2a with an acid catalyst, suggesting that the cis-isomer is more thermodynamically stable than the trans-isomer. With ZnF2/SbCl5 the cis-isomer was barely detected (run 11, Table 3). The ratio of trans-2a:cis-2a:PhSF5 was 385:0:100 after 10 min; 63:trace

An efficient and practical entry to 2-amido-dienes and 3-amido-trienes from allenamides through stereoselective 1,3-hydrogen shifts

• Ryuji Hayashi,
• John B. Feltenberger,
• Andrew G. Lohse,
• Mary C. Walton and
• Richard P. Hsung

Beilstein J. Org. Chem. 2011, 7, 410–420, doi:10.3762/bjoc.7.53

• thermal isomerization of exocyclic allenes to dienes via radical intermediates see [4][5][6][7][8][9][10][11][12]), whereby controlling E/Z ratios of the resulting diene remains a difficult problem. On the other hand, a stepwise isomerization of allenes via acid-, base-, or metal-mediated conditions seem

• argument could be used to rationalize the regioselective 1,3-hydrogen shift when acid was used. It is noteworthy that this charged transition state could also be adopted for the thermal isomerization. While still being a neutral transition state, the nitrogen atom could facilitate a polarized transition