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ADVANCED SYNTHESIS & CATALYSIS · 2021 ·Vol. 363 ·期 6 ·1672-1684 · IF 5.837

Rh(III)-Catalyzed Csp2−Csp3 Bond Cleavage/Carbonylethylation of α-Indolyl Alcohols

Zhipeng Liu,Xinwei Hu,Can Yang,Haisheng Xie,Huanfeng Jiang,Wei Zeng

Graphical A Rh(III)-catalyzed C sp 2 −C sp 3 bond cleavage/carbonylethylation of α-indolyl alcohols with allylic alcohols has been reported. This transformation involved a cascade C−C bond cleavage/C−C bond formation, and provides a novel approach to assemble 2-carbonylethylindole skeletons.

研究领域: 有机化学 · 催化反应
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ORGANIC & BIOMOLECULAR CHEMISTRY · 2014 ·Vol. 12 ·期 21 ·3493-3498 · IF 3.487

Direct olefination of benzaldehydes into 1,3-diarylpropenes via a copper-catalyzed heterodomino Knoevenagel-decarboxylation-Csp3-H activation sequence

Yaping Zhao,Lu Sun,Tieqiang Zeng,Jiayi Wang,Yanqing Peng,Gonghua Song

Copper-catalyzed direct olefination of benzaldehydes into 1,3-diarylpropenes by a novel domino Knoevenagel-decarboxylation-Csp3-H activation sequence is reported. This method provides a concise and effective route toward the synthesis of unsymmetrical 1,3-diarylpropene derivatives.

CAS / MDL: 1317-38-0
研究领域: 有机化学 · 催化化学
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Science Advances · 2020 ·Vol. 6 ·期 45 · IF 13.117

Selective valorization of lignin to phenol by direct transformation of Csp2–Csp3 and C–O bonds

Jiang Yan,Qinglei Meng,Xiaojun Shen,Bingfeng Chen,Yang Sun,Junfeng Xiang,Huizhen Liu,Buxing Han

Phenol is an important commodity chemical in the industry, which is currently produced using fossil feedstocks. Here, we report a strategy to produce phenol from lignin by directly deconstructing C sp2 –C sp3 and C–O bonds under mild conditions. It was found that zeolite catalyst could efficiently catalyze both the direct C sp2 –C sp3 bond breakage to remove propyl structure and aliphatic β carbon–oxygen (C β– O) bond hydrolysis to form OH group on the aromatic ring. The yield of phenol could reach 10.9 weight % with a selectivity of 91.8%. In this unique route, water was the only reactant besides lignin. A scale-up experiment showed that 4.1 g of pure phenol could be obtained from 50.0 g of lignin. The reaction pathway was proposed by a combination of control experiments and density functional theory studies. This work opens the way for producing phenol from lignin by direct transformation of C sp2 –C sp3 and C–O bonds in lignin.

研究领域: 催化 · 绿色化学 · 生物质转化 · 化学工程 · 有机化学
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PESTICIDE BIOCHEMISTRY AND PHYSIOLOGY · 2024 · IF 4.2

Three chemosensory proteins enriched in antennae and tarsi of Rhaphuma horsfieldi differentially contribute to the binding of insecticides

Yu-Juan Yao,Ning-Na Yin,Lin-Mei Pu,An-Jing Yang,Nai-Yong Liu

Antennae and legs (primarily the tarsal segments) of insects are the foremost sensory organs that contact a diverse range of toxic chemicals including insecticides. Binding proteins expressed in the two tissues are potential molecular candidates serving as the binding and sequestering of insecticides, like chemosensory proteins (CSPs). Insect CSPs endowed with multiple roles have been suggested to participate in insecticide resistance , focusing mainly on moths, aphids and mosquitos. Yet, the molecular underpinnings underlying the interactions of cerambycid CSPs and insecticides remain unexplored. Here, we present binding properties of three antenna- and tarsus-enriched RhorCSPs (RhorCSP1, CSP2 and CSP3) in Rhaphuma horsfieldi to eight insecticide classes totaling 15 chemicals. From the transcriptome of this beetle, totally 16 CSP-coding genes were found, with seven full-length sequences. In phylogeny, these RhorCSPs were distributed dispersedly in different clades. Expression profiles revealed the abundant expression of RhorCSP1 , CSP2 and CSP3 in antennae and tarsi, thus as representatives for studying the protein-insecticide interactions. Binding assays showed that the three RhorCSPs were tuned differentially to insecticides but exhibited the highest affinities with hexaflumuron, chlorpyrifos and rotenone (dissociation constants <13 μM). In particular, RhorCSP3 could interact strongly with 10 of tested insecticides, of which four residues (Tyr25, Phe42, Val65 and Phe68) contributed significantly to the binding of six, four, three and four ligands, respectively. Of these, the binding of four mutated RhorCSP3s to a botanical insecticide rotenone was significantly weakened compared to the wildtype protein. Furthermore, we also evidenced that RhorCSP3 was a broadly-tuned carrier protein in response to a wide variety of plant odorants outside insecticides. Altogether, our findings shed light on different binding mechanisms and odorant-tuning profiles of three RhorCSPs in R. horsfieldi and identify key residues of the RhorCSP3-insecticide interactions.

研究领域: 昆虫学 · 分子生物学 · 生物化学 · 昆虫毒理学
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