Polar Diels–Alder reactions using electrophilic nitrobenzothiophenes. A combined experimental and DFT study

• Polar Diels–Alder reaction using nitrobenzothiophenes.
• Theoretically studies using DFT.
• The reaction of nitrobenzothiophenes and a diene are a domino process.
• The reaction irreversibility is connect with the loss of nitrous acid.
• The most favorable regioisomeric channels are associated with C3–C4.

The reactions between 2- and 3-nitrobenzothiophenes with three dienes of different nucleophilicity, 1-methoxy-3-trimethylsilyloxy-1,3-butadiene, 1-trimethylsilyloxy-1,3-butadiene and isoprene developed in anhydrous benzene and alternative under microwave irradiation with molecular solvents or in free solvent conditions, respectively, for produce dibenzothiophenes permit to conclude that both nitroheterocycles act as electrophile with the cited dienes. In the cases of the dienes 1-methoxy-3-trimethylsilyloxy-1,3-butadiene and 1-trimethylsilyloxy-1,3-butadiene which posses major nucleophilicity the observed product is the normal cycloaddition one. However when the diene is isoprene the product with both electrophiles follow the hetero Diels–Alder way. These reactions are considered polar cycloaddition reactions and the yields are reasonables. Moreover the polar Diels–Alder reactions of nitrobenzothiophenes with electron rich dienes 1-trimethylsilyloxy-1,3-butadiene have been theoretically studied using DFT methods.

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