甘油酸
立体中心
化学
催化作用
木糖
外消旋化
劈理(地质)
异构化
有机化学
药物化学
对映选择合成
立体化学
材料科学
断裂(地质)
复合材料
发酵
作者
Ruofeng Yang,Shuguang Xu,Xiaoyan Wang,Yuan Xiao,Jianmei Li,Changwei Hu
标识
DOI:10.1002/ange.202403547
摘要
Abstract Chiral carboxylic acid production from renewable biomass by chemocatalysis is vitally important for reducing our carbon footprint, but remains underdeveloped. We herein establish a strategy that make use of a stereogenic center of biomass to achieve a rare example of D‐glyceric acid production with the highest yield (86.8 %) reported to date as well as an excellent ee value (>99 %). Unlike traditional asymmetric catalysis, chiral catalysts/additives are not required. Ample experiments combined with quantum chemical calculations established the origins of the stereogenic center and catalyst performance. The chirality at C4 in D‐xylose was proved to be retained and successfully delivered to C2 in D‐glyceric acid during C−C cleavage. The remarkable cooperative‐roles of Ag + and Ag 0 in the constructed Ag/γ‐Al 2 O 3 catalyst are disclosed as the crucial contributors. Ag + was responsible for low‐temperature activation of D‐xylose, while Ag 0 facilitated the generation of active O* from O 2 . Ag + and active O* cooperatively promoted the precise cleavage of the C2−C3 bond, and more importantly O* allowed the immediate fast oxidization of the D‐glyceraldehyde intermediate to stabilize D‐glyceric acid, thereby inhibiting the side reaction that induced racemization. This strategy makes a significant breakthrough in overcoming the limitation of poor enantioselectivity in current chemocatalytic conversion of biomass.
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