Organophotoredox-Catalyzed Stereoselective Synthesis of Bicyclo[3.2.0]heptanes via [2+2] Photocycloaddition

有机光氧化还原催化的[2+2]光环加成反应立体选择性合成双环[3.2.0]庚烷

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Abstract

The stereoselective synthesis of bicyclo[3.2.0]heptanes via an anion radical [2+2] photocycloaddition of aryl bis-enone derivatives was investigated. By employing chiral oxazolidinone auxiliaries bound to aryl bis-enone substrates, enantioenriched, highly substituted bicyclo[3.2.0]heptanes have been synthesized. The reaction, mediated by Eosin Y and promoted by LiBr under visible light irradiation, has been studied both experimentally and computationally to elucidate the mechanism and stereoselective outcomes. The process proceeds via a syn-closure pathway, leading to the formation of the corresponding cis-anti diastereoisomers as major products isolated and characterized by X-ray analysis; DFT calculations provided useful insights and computational support which allow a plausible reaction mechanism to be proposed that agrees with the collected experimental data.

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