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Selective photocatalytic hydroxylation and epoxidation reactions by an iron complex using water as the oxygen source
Chemical Science ( IF 7.6 ) Pub Date : 2017-09-04 00:00:00 , DOI: 10.1039/c7sc02780j Bittu Chandra 1, 2, 3 , Kundan K. Singh 1, 2, 3 , Sayam Sen Gupta 1, 2, 3
Chemical Science ( IF 7.6 ) Pub Date : 2017-09-04 00:00:00 , DOI: 10.1039/c7sc02780j Bittu Chandra 1, 2, 3 , Kundan K. Singh 1, 2, 3 , Sayam Sen Gupta 1, 2, 3
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The iron complex [(bTAML)FeIII–OH2]− (1) selectively catalyses the photocatalytic hydroxylation and epoxidation reactions of alkanes and alkenes, respectively, using water as the oxygen-atom source. Upon the oxidation of unactivated alkanes, which included several substrates including natural products, hydroxylation was observed mostly at the 3° C–H bonds with 3°
:2° selectivity up to ∼100:1. When alkenes were used as the substrates, epoxides were predominantly formed with high yields. In the presence of H218O, more than 90% of the 18O-labelled oxygen atoms were incorporated into the hydroxylated and epoxide product indicating that water was the primary oxygen source. Mechanistic studies indicate the formation of an active [{(bTAML)FeIV}2-μ-oxo]2− (2) dimer from the starting complex 1 via PCET. The subsequent disproportionation of 2 upon addition of substrate, leading to the formation of FeV(O), renders the high selectivity observed in these reactions.
中文翻译：
铁配合物以水为氧源的选择性光催化羟基化和环氧化反应
铁络合物[（bTAML）Fe III -OH 2 ] -（1）分别使用水作为氧原子源，分别选择性催化烷烃和烯烃的光催化羟基化和环氧化反应。在未活化的烷烃被氧化后，其中包括几种包括天然产物在内的底物，大多数情况下在3°C–H键上观察到羟基化，选择性高达3：2 ：2，直至约100 ：1。当使用烯烃作为底物时，环氧化物主要以高产形成。在H存在2 18 O，90％以上的的18O标记的氧原子被掺入羟基化和环氧产物中，表明水是主要的氧源。机理研究表明，起始的复合物1通过PCET形成了活性的[{（bTAML）Fe IV } 2 - μ-氧代] 2-（2）二聚体。添加底物时随后的歧化2导致形成Fe V（O），从而在这些反应中观察到高选择性。
更新日期：2017-09-22
:2° selectivity up to ∼100:1. When alkenes were used as the substrates, epoxides were predominantly formed with high yields. In the presence of H218O, more than 90% of the 18O-labelled oxygen atoms were incorporated into the hydroxylated and epoxide product indicating that water was the primary oxygen source. Mechanistic studies indicate the formation of an active [{(bTAML)FeIV}2-μ-oxo]2− (2) dimer from the starting complex 1 via PCET. The subsequent disproportionation of 2 upon addition of substrate, leading to the formation of FeV(O), renders the high selectivity observed in these reactions.
中文翻译：
铁配合物以水为氧源的选择性光催化羟基化和环氧化反应
铁络合物[（bTAML）Fe III -OH 2 ] -（1）分别使用水作为氧原子源，分别选择性催化烷烃和烯烃的光催化羟基化和环氧化反应。在未活化的烷烃被氧化后，其中包括几种包括天然产物在内的底物，大多数情况下在3°C–H键上观察到羟基化，选择性高达3
：2 ：2，直至约100 ：1。当使用烯烃作为底物时，环氧化物主要以高产形成。在H存在2 18 O，90％以上的的18O标记的氧原子被掺入羟基化和环氧产物中，表明水是主要的氧源。机理研究表明，起始的复合物1通过PCET形成了活性的[{（bTAML）Fe IV } 2 - μ-氧代] 2-（2）二聚体。添加底物时随后的歧化2导致形成Fe V（O），从而在这些反应中观察到高选择性。
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