An Unprecedented [2+3] Cycloadditive Dimerization of a Transient Thiocarbonyl S‐Ylide

Abstract

Keywords: Cycloaddition / Ab initio calculations / Sulfur / Ylides 4-Chlorophenyl C-(phenylsulfonyl)dithioformate reacts with diazo(trimethylsilyl)methane to form 2-(4-chlorophenylthio)-2-phenylsulfonyl-4,5-bis(trimethylsilyl)-1,3-dithiolan-1-ium (4-chlorophenylthio)(phenylsulfonyl)methylide. It is assumed that this product is formed by [2+3] cycloadditive dimeriz-

Computational Study of a Model System of Enzyme-Mediated [4+2] Cycloaddition Reaction

“…The increase of molecular complexity led to a more pronounced asynchrony of the C-C bonds formation. The result is in a good agreement with the earlier DFT calculations of the [4+2] transition states [ 41 , 42 , 43 , 44 , 45 , 46 , 83 ].…”

1,4‐Dioxo‐1,4‐dihydronaphthalene‐2,3‐dicarbonitrile and 1,1,2,2‐Tetracyanoethene in Heterocyclization

“…Senning and coworkers reported on an unexpected dimerization of a thiocarbonyl S ‐methanide ( 168 ), which was generated by treatment of an aryl C ‐(phenylsulfonyl)dithioformate ( 166 ) with diazomethane ( 167 ) . The highly reactive TCNE 2 underwent a smooth [2 + 3]cycloaddition with 168 to give the racemic tetrahydrothiophene 169 in 34% yield (Scheme ) .…”

Sulfur, An Important Element in my Life

“…In this cycloaddition one molecule of 262 plays the role of a 1,3-dipole and another molecule of 262 serves as dipolarophile [156].…”