Controllable and mild photoenzymatic production of chiral alcohols was realized by coupling a versatile photochemical NAD(P)H regeneration system with (R)- or (S)-selective ketoreductases. The efficiency of NAD(P)H regeneration was improved using a Rhodium functionalized metal organic framework, namely Rh-UiO-67, to adjust and control electron transport and electron utilization. Furthermore, six different ketoreductases could be successfully immobilized on Rh-UiO-67 and combined with the light-driven NAD(P)H regeneration system to produce chiral aryl alcohols. Various chiral alcohols with complementary (R)- and (S)-conformations can be constructed by this method with high yields (97%) and excellent stereoselectivity (>99% ee).
Shengnan Zhao,Song Song,Yong You,Yingtian Zhang,Wei Luo,Kaijie Han,Tong Ding,Ye Tian,Xingang Li
Heterogeneous photocatalytic C-C coupling is a green and efficient approach to producing valuable chemicals. The strategies for guiding effective photocatalyst design are desired but still limited. Here, we report visible-light-driven highly selective photocatalytic C-C coupling of benzyl alcohol over surfactant-modified Zn 3 In 2 S 6 semiconductors. A complete switch of product selectivity from benzyl aldehyde (91.5 %) to C-C coupling products (96.5 %) is obtained by the modification of Zn 3 In 2 S 6 with stearyl trimethyl ammonium bromide (STAB). This modification assists the formation of sulfur vacancies on Zn 3 In 2 S 6 to enhance charge carrier separation, thereby increasing the photocatalytic activity. The selectivity switch is mainly attributed to increasing conduction band position of Zn 3 In 2 S 6 by surfactant modification which strengthens the reduction ability of photogenerated electrons to induce the reversible reduction of benzyl aldehyde to ketyl radicals, and partially to the poor oxidation ability of the material that inhibits the oxidation of ketyl radicals to benzyl aldehyde. Encouragingly, this universal protocol has been successfully applied to a series of aromatic alcohols and biomass-derived furanic alcohols to selectively produce C-C coupling products.