ADVANCED SYNTHESIS & CATALYSIS
·
2021
·Vol. 363
·期 6
·1672-1684
·
IF 5.837
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
✓ 已验证
DOI
高影响因子
Science China-Chemistry
·
2023
·Vol. 67
·期 1
·374-382
·
IF 9.6
Luo Zhongfeng,Jiang Jingxing,Zou Lifang,Zhou Xiaoyu,Liu Junshan,Ke Zhuofeng,Chen Fengjuan,Jiang Huanfeng,Zeng Wei
We disclose the development of the Rh-catalyzed amine-directed remote 5,6-carboamination protocol of pyridines via dual Csp 2 –H functionalizations. A variety of readily available 2-aminopyridines and 1,2,3-triazoles are allowed for coupling cyclization to access polyfunctionalized azaindoles. Mechanistic studies including DFT calculations unveil that relay carbenoid-electrophilic addition to pyridines and the sequential pyridyl Csp 2 –H amination are involved in this transformation. The post-synthetic utility of this methodology is showcased by versatile and site-selective modification of azaindoles.
研究领域:
有机化学
·
催化化学
✓ 已验证
DOI
高影响因子
JOURNAL OF ORGANIC CHEMISTRY
·
2025
·
IF 3.6
Jingru Zou,Lingmeng Xie,Wen Qin,Xingang Xie,Xing Huo
The Groebke–Blackburn–Bienaymé (GBB) reaction provides efficient access to imidazole-fused heterocycles, yet it is inevitably endowed with an isocyanide-derived secondary amino group in products. Herein, we report a Pd(II)-catalyzed sp2 C–H carbonylative amidation strategy using Co2(CO)8 as a safe CO surrogate. Leveraging the native aryl amino group as a directing motif, this protocol enables direct conversion of GBB adducts into pharmaceutically relevant imidazo[1,2-a]pyridine-fused δ-lactams with up to 86% yield. The method demonstrates exceptional functional group tolerance and eliminates prefunctionalization requirements, offering a streamlined approach to access complex nitrogen-rich architectures.
研究领域:
有机化学
·
药物化学
·
杂环化学
·
转化医学
·
分子药理学
✓ 已验证
DOI
PubMed
高影响因子
Science Advances
·
2020
·Vol. 6
·期 45
·
IF 13.117
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
✓ 已验证
DOI
高影响因子
INSECT BIOCHEMISTRY AND MOLECULAR BIOLOGY
·
2026
·
IF 4.3
Fu-Peng Li,Xiao-Rong Xiong,Zi-Hui Liu,Zi-Hao Long,Lin-Mei Pu,Nai-Yong Liu
Behaviorally active compounds of longhorned beetles, including sex/aggregation pheromones and plant odorants, have been extensively applied to the integrated pest management. It is largely unknown, however, how beetle's chemosensory proteins (CSPs) mediate the detection of semiochemicals. Here, we characterized six antenna-enriched PantCSPs in Pharsalia antennata , revealing the strong binding to two floral scents syringaldehyde and β-ionone (dissociation constant, K i < 5.5 μM). In particular, PantCSP11 presented the binding preference to 11–12C aliphatic alcohols/aldehydes (K i = 0.96 ± 0.02 μM–5.55 ± 0.11 μM) and 6C green leaf volatiles (K i = 5.07 ± 0.24 μM–11.60 ± 0.07 μM). It was worth noting that a male-antenna-biased PantCSP2 and its 10 orthologs from other 10 cerambycid species played a crucial role in the detection of sex/aggregation pheromones. This pheromone analogue pseudoionone tuned to by 11 CSP2 proteins (K i < 9.6 μM) may be developed as the component or synergist of cerambycid generic lures. Further, six PantCSPs and 11 CSP2 orthologs could interact strongly with broad-spectrum insecticides, particularly chlorpyrifos and phoxim (K i < 4.8 μM). We identified 10 key residues involved in the interactions of MaltCSP3 in Monochamus alternatus and chemicals, and meanwhile demonstrated an essential role of two conserved binding sites (Gln61 and Thr65/Ser65) among CSP2 orthologs in the specific recognition of key chemicals. This study enhances our knowledge in understanding CSP-mediated odorant and pheromone detection in Cerambycidae and provides insights into adaptive evolution of beetles in the context of insecticide use.
✓ 已验证
产品关联
DOI
PubMed
高影响因子
PESTICIDE BIOCHEMISTRY AND PHYSIOLOGY
·
2024
·
IF 4.2
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
✓ 已验证
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）