摘要：ZengruiCheng1†, Kaimeng Huang1,2†, Chen Wang1†, Lili Chen1†, Xinyao Li3, Zhibin Hu1, Xinyuan Shan4, Peng-Fei Cao4, Haofeng Sun5, W

转自：康龙化成

Catalytic Remodeling of Complex Alkenes to Oxonitriles Through C=C Double Bond Deconstruction

ZengruiCheng1†, Kaimeng Huang1,2†, Chen Wang1†, Lili Chen1†, Xinyao Li3, Zhibin Hu1, Xinyuan Shan4, Peng-Fei Cao4, Haofeng Sun5, Wei Chen6, Chenhao Li2, Ziyao Zhang1, Hui Tan1, Xue Jiang1, Guikai Zhang7, Zhongying Zhang7, Min Lin2, Liang Wang8, Anmin Zheng6,9, Changjiu Xia2*, TengWang4, Song Song1, Xingtian Shu2, Ning Jiao1,10*

1StateKey Laboratory of Natural and Biomimetic Drugs, Chemical Biology Center, Schoolof Pharmaceutical Sciences, Peking University, Beijing, China.

2State Key Laboratory of CatalyticMaterials and Reaction Engineering, Research Institute of Petroleum Processing,SINOPEC, Beijing, China.

3Shanghai University.

4Beijing University of ChemicalTechnology.

5University of Science and Technology ofChina.

6Chinese Academy of Sciences, Wuhan,China.

7University of Chinese Academy ofSciences.

8Zhejiang University.

9Wuhan University of Science andTechnology.

10Changping Laboratory, Beijing, China.

†These authors contributed equally to this work

—Science 2025, 10.1126/science.adq8918

Recommended by Rui Jin _ MC5

KEYWORDS: carbon-carbon double bonds Cleavage, aerobic nitrogenation,skeletal editing (反应类型),C(sp2)=O, C(sp)≡N (成键类型), alkenes (原料), oxonitriles (产物), CuO/h-TS-1,TMSN3, oxygen, heterogeneous catalysis, catalyst recycling (其他)

ABSTRACT: Deconstructive transformation of carbon-carbon double bonds (C=C) is a pivotal strategy in synthetic chemistry and drug discovery. Despite the substantial advances in olefin metathesis and ozonolysis for natural product synthesis through C=C double-bond cleavage, the catalytic remodeling of complex molecules through C=C double-bond deconstruction has been underdeveloped. Ning jiao and Changjiu Xia et al. report a heterogeneous copper-catalyzed C=C double-bond cleavage, which enables the remodeling of complex molecules by converting the carbons on either side of the C=C double bond to carbonyl and cyano groups, respectively. In particular, thismethod provides an efficient protocol to conveniently transform Terpenoids, glycals, Steroids, and bioactive molecules to privileged scaffolds with underexplored chemical space.

Background and this work:Cleavage of C=C double bonds

Screening of reaction conditions

TEM images of CuO/h-TS-1

Olefin scope: heterogeneous catalytic aerobic nitrogenation(selected examples)

Modification of bioactive molecules(selected examples): (A) Steroids; (B) Terpenoids; (C) Glycals.

Proposed mechanism

Prof.Ning jiao and Changjiu Xia et al.reported aheterogeneous copper-catalyzed C=C double-bond cleavage,which enables the remodeling of complex molecules by convertingthe carbons on either side of the C=C double bond to carbonyl and cyano groups,respectively. Inparticular, thismethod provides an efficient protocol to conveniently transform terpenoids, glycals,steroids, and bioactive molecules to privileged scaffolds with underexploredchemical space. This chemistry provides a powerful protocol to build compoundlibraries with expanded chemical space and substantially enlarges the frontierof synthetic chemistry and drug discovery.

北京大学焦宁教授和中国石化石油化工科学研究院夏长久研究员团队报道了一种由空心钛硅分子筛负载的氧化铜（CuO/h-TS-1）非均相催化的C=C双键断裂方法，将C=C双键两侧的碳分别转化为羰基和氰基，实现了复杂分子的重塑。该方法提供了一种高效地将萜类、糖类、类固醇等生物活性分子转化为新化合物的方案，为构建具有扩展化学空间的化合物库提供了强有力的工具，极大地拓展了合成化学和药物发现的前沿领域。

来源：新浪财经