Radical cation Diels-Alder reactions provide a powerful method for the construction of six-membered ring systems between both electron-rich dienes and dienophiles. However, the most recent examples of this class have ...Radical cation Diels-Alder reactions provide a powerful method for the construction of six-membered ring systems between both electron-rich dienes and dienophiles. However, the most recent examples of this class have been limited to β-methylstyrenes as dienophiles;the use of non-conjugated alkenes remains challenging. The present study describes the serendipitous development of novel radical cation Diels-Alder reactions by electrocatalysis that use non-conjugated alkenes as dienophiles. The key to successful transformation involves highly substituted cyclohexenyl radical cations that are stable enough to be reduced by intermolecular single electron transfer.展开更多
The discovery that lithium bis(trifluoromethane)sulfonamide (LiTFSI)/1-nitropropane (PrNO2) solution functions as a less polar alternative to lithium perchlorate (LiClO4)/nitromethane (MeNO2) solution has led to the d...The discovery that lithium bis(trifluoromethane)sulfonamide (LiTFSI)/1-nitropropane (PrNO2) solution functions as a less polar alternative to lithium perchlorate (LiClO4)/nitromethane (MeNO2) solution has led to the development of a novel thermomorphic system for electrocatalytic Diels-Alder reactions. Methyl cyclohexane (Me-c-Hex) can form a monophasic condition with LiTFSI/PrNO2 solution at room temperature, enabling the use of hydrophobic dienophiles. After the electrochemical reaction, a biphasic condition can be formed at –50℃, where the cycloadducts are selectively recovered from the upper Me-c-Hex phase and the remaining lower LiTFSI/PrNO2 solution can be reused.展开更多
文摘Radical cation Diels-Alder reactions provide a powerful method for the construction of six-membered ring systems between both electron-rich dienes and dienophiles. However, the most recent examples of this class have been limited to β-methylstyrenes as dienophiles;the use of non-conjugated alkenes remains challenging. The present study describes the serendipitous development of novel radical cation Diels-Alder reactions by electrocatalysis that use non-conjugated alkenes as dienophiles. The key to successful transformation involves highly substituted cyclohexenyl radical cations that are stable enough to be reduced by intermolecular single electron transfer.
文摘The discovery that lithium bis(trifluoromethane)sulfonamide (LiTFSI)/1-nitropropane (PrNO2) solution functions as a less polar alternative to lithium perchlorate (LiClO4)/nitromethane (MeNO2) solution has led to the development of a novel thermomorphic system for electrocatalytic Diels-Alder reactions. Methyl cyclohexane (Me-c-Hex) can form a monophasic condition with LiTFSI/PrNO2 solution at room temperature, enabling the use of hydrophobic dienophiles. After the electrochemical reaction, a biphasic condition can be formed at –50℃, where the cycloadducts are selectively recovered from the upper Me-c-Hex phase and the remaining lower LiTFSI/PrNO2 solution can be reused.
