American Chemical Society
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π-Face-Selective Diels−Alder Reactions of 3,4-Di-tert-butylthiophene 1-Oxide and 1-Imide and Formation of 1,2-Thiazetidines

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journal contribution
posted on 2003-06-12, 00:00 authored by Takashi Otani, Jun Takayama, Yoshiaki Sugihara, Akihiko Ishii, Juzo Nakayama
3,4-Di-tert-butylthiophene 1-oxide (1a) reacted with a series of electron-deficient alkenic dienophiles at its syn-π-face relating to the SO bond to give [4+2] adducts in excellent yields. The 1-oxide 1a also reacted even with angle-strained dienophiles acenaphthylene and norbornene at its syn-π-face to afford [4+2] adducts; in the latter case, norbornene reacted exclusively at its exo-π-face. The oxide 1a reacted with dimethyl acetylenedicarboxylate to produce dimethyl 4,5-di-tert-butylphthalate in high yield with spontaneous extrusion of SO from the initial adduct even at room temperature. Similarly, 3,4-di-tert-butylthiophene 1-(p-toluenesulfonyl)imide (3a) reacted with alkenic dienophiles at its syn-π-face relating to the SN bond to give [4+2] adducts in good yields. The reaction of 3a with 4-phenyl-1,2,4-triazoline-3,5-dione (PTAD) afforded a 1,2-thiazetidine 12a, the first example of S-unoxidized 1,2-thiazetidine, in good yield, through rearrangement of the initial [4+2] adduct. The molecular structure of 12a is discussed on the basis of the X-ray crystallographic analysis. Comparison of the foregoing reactions leads to the conclusion that the 1-oxide 1a is more reactive as a diene than the 1-imide 3a, which is more reactive than 3,4-di-tert-butylthiophene 1,1-dioxide. The origin of the syn-π-face selectivities of 1a and 3a in Diels−Alder reactions is discussed in terms of the orbital mixing rule and steric effect and also based on B3LYP/6-31G(d) calculations.