Co-reporter:Xue Tian;Chao Zhang;Qi Xu;Zhong Li;Xusheng Shao
Organic & Biomolecular Chemistry 2017 vol. 15(Issue 15) pp:3320-3323
Publication Date(Web):2017/04/11
DOI:10.1039/C6OB02813F
Benzoylphenylureas (BPUs) are used as synthetic insect growth regulators for inhibiting chitin synthesis. Merging insecticidal BPUs with photoswitchable azobenzene generated photoresponsive chitin synthesis inhibitors. A prepared azobenzene-benzoylphenylurea can be activated upon irradiation with UV light, and shows 6-fold and 2-fold activity difference to armyworm (Mythimna separata) and German cockroach (Blattella germanica) sulfonylurea receptors, respectively. This is the first example of a photoswitchable BPU insecticide. The generation of such a photoresponsive BPU insecticide allows for modulation of the insecticidal activity by light, and may facilitate the spatiotemporal control over the sulfonylurea receptor and the mechanistic study of this kind of insecticide.
Co-reporter:Zhenhong Gao, Pengtao Yuan, Donghui Wang, Zhiping Xu, Zhong Li, Xusheng Shao
Bioorganic & Medicinal Chemistry Letters 2017 Volume 27, Issue 11(Issue 11) pp:
Publication Date(Web):1 June 2017
DOI:10.1016/j.bmcl.2017.03.091
Developing efficient controlled release system of insecticide can facilitate the better use of insecticide. We described here a first example of photo-controlled release of an insecticide by linking fipronil with photoresponsive coumarin covalently. The generated coumarin-fipronil (CF) precursor could undergo cleavage to release free fipronil in the presence of blue light (420 nm) or sunlight. Photophysical studies of CF showed that it exhibited strong fluorescence properties. The CF had no obvious activity against mosquito larvae under dark, but it can be activated by light inside the mosquito larvae. The released Fip from CF by blue light irradiation in vitro retained its activity to armyworm (Mythimna separate) with LC50 value of 24.64 μmol L−1. This photocaged molecule provided an alternative delivery method for fipronil.Download high-res image (78KB)Download full-size image
Co-reporter:Ya-Nan Zhang, Yi-An Feng, Zhong Li, Xu-Sheng Shao
Chinese Chemical Letters 2017 Volume 28, Issue 6(Volume 28, Issue 6) pp:
Publication Date(Web):1 June 2017
DOI:10.1016/j.cclet.2017.04.003
Phenalenone is a kind of defensive compound biosynthesized inside plants in response to the outside attack such as fungus and nematodes. A set of derivatives encompassing structural modifications on the privileged phenalenone scaffold were synthesized through introduction of phenyl and hydroxyl substitutes at 9-positon and 2-position and assessed their insecticidal activities against armyworm (Mythimna separata Walker) and cowpea aphids (Aphis craccivora). No obvious insecticidal activities of the synthesized compounds were observed against armyworm. Some of the 9-phenyl and 2-hydroxy substituted phenalenone analogues showed potential activities against cowpea aphids with 33%–41% mortality at 500 mg/L.Download high-res image (123KB)Download full-size imageA set of derivatives encompassing structural modifications on the privileged phenalenone scaffold were synthesized through introduction of phenyl and hydroxyl substitutes at 9-positon and 2-position and assessed their insecticidal activities against armyworm (Mythimna separata Walker) and cowpea aphids (Aphis craccivora).
Co-reporter:Qing-Qing Hou, Yi-Fei Jing, Xu-Sheng Shao
Chinese Chemical Letters 2017 Volume 28, Issue 8(Volume 28, Issue 8) pp:
Publication Date(Web):1 August 2017
DOI:10.1016/j.cclet.2017.05.016
1,8-Naphthyridines (NAP) are biological important scaffolds in bioactive molecules design. By hybrid of NAP with neonicotinoid core structure, nine novel NAP derivatives were synthesized and subjected to insecticidal activities evaluation. Some of the compounds showed excellent insecticidal activity against cowpea aphids (Aphis craccivora) with LC50 values ranging from 0.011 mmol/L to 0.067 mmol/L. The results indicated that 1,8- naphthyridine can be used as insecticidal structure for further modification.1,8-Naphthyridines (NAP) are biological important scaffolds in bioactive molecules design. By hybrid of NAP with neonicotinoid core structure, nine novel NAP derivatives were synthesized and subjected to insecticidal activities evaluation. Some of the compounds showed excellent insecticidal activity against cowpea aphids (Aphis craccivora) with LC50 values ranging from 0.011 mmol/L to 0.067 mmol/L. The results indicated that NAP can be used as insecticidal structure for further modification.Download high-res image (125KB)Download full-size image
Co-reporter:Feilong Sun, Xusheng Shao and Zhong Li
RSC Advances 2016 vol. 6(Issue 19) pp:15382-15389
Publication Date(Web):01 Feb 2016
DOI:10.1039/C5RA23393C
An efficient and concise method was developed for access to indenofurans and indenopyridines through a one pot, three-component protocol from heterocyclic ketene aminals, o-phthalaldehyde and 1,3-diketones under catalyst-free conditions. The indenofurans and indenopyridines were formed via aldol condensation, a regioselective aza–ene reaction, imine–enamine tautomerization and intramolecular cyclization.
Co-reporter:Ye Liu, Chao Lei, Xiao-Yong Xu, Xu-Sheng Shao, Zhong Li
Chinese Chemical Letters 2016 Volume 27(Issue 3) pp:321-324
Publication Date(Web):March 2016
DOI:10.1016/j.cclet.2015.12.011
Diamides acting on insect ryanodine receptors are an intensive research area now. In order to search for novel candidates, a series of diamides containing biphenyl substructure were designed and synthesized. Their insecticidal activities against armyworms (Mythimna sepatara) and aphis (Aphis craccivora) were screened. The compounds with 3,5-dichloro-4-(1,1,2,2-tetrafluoroethoxy)phenyl substituent were found to be insecticidal to armyworms with the similar symptoms to poisoning by flubendiamide. In this research, we presented a novel type of diamide insecticide as a lead compound for further optimization.A series of novel diphenic diamides were designed and synthesized. The insecticidal activities were assayed to give potential candidates.
Co-reporter:Shen Li, Run-Jiang Song, Dong-Hui Wang, Xue Tian, Xu-Sheng Shao, Zhong Li
Chinese Chemical Letters 2016 Volume 27(Issue 5) pp:635-639
Publication Date(Web):May 2016
DOI:10.1016/j.cclet.2016.03.033
A series of imidacloprid derivatives containing an azopyridine motif as a photoswitchable functional group were designed and synthesized. The new version of photoresponsive imidacloprid analogues showed improved solubility in comparison with their azobenzene analogues. 1.2 to 2-fold activity difference was observed for these azopyridine-imidacloprids against house fly (Musca domestica) and cowpea aphid (Aphis craccivora) upon irradiation.A series of imidacloprid derivatives containing an azopyridine motif as a photoswitchable functional group were designed and synthesized. The new version of photoresponsive imidacloprid analogues showed improved solubility in comparison with their azobenzene-imidacloprid analogues. 1.1-2-fold activity difference was observed for these azopyridine-imidacloprids against house fly (Musca domestica) and cowpea aphid (Aphis craccivora) upon irradiation.
Co-reporter:Jiling Li, Dang Wu, Xiaoyong Xu, Jin huang, Xusheng Shao, Zhong Li
Bioorganic & Medicinal Chemistry Letters 2016 26(13) pp: 3064-3066
Publication Date(Web):1 July 2016
DOI:10.1016/j.bmcl.2016.05.016
A series of 1,3-benzoazole derivatives possessing amide moieties were designed, synthesized and evaluated as inhibitors against human dihydroorotate dehydrogenase (hDHODH). Compounds A11, A14 and A26 exhibited good to excellent activities against hDHODH at the concentration of 10 μM. In particular, compound A14 displayed an IC50 value of 0.178 μM with 2-fold preference over A771726. The result implied that a proper degree of steric size and electron density of the C-6 amide moiety was necessary to retain the inhibitory activity of the synthesized compounds.
Co-reporter:Yian Feng, Minming Zou, Runjiang Song, Xusheng Shao, Zhong Li, and Xuhong Qian
The Journal of Organic Chemistry 2016 Volume 81(Issue 21) pp:10321-10327
Publication Date(Web):August 25, 2016
DOI:10.1021/acs.joc.6b01307
A method for preparation of 1,4,2-dithiazolidine or 1,3-thiazetidine heterocycles was developed by reactions of phenylthioureas with 1,1-dichloro-2-nitroethene. The solvent has a significant influence on the type of product formation. 1,4,2-Dithiazolidines were formed in the aprotic solvent chloroform, while in the protic solvent ethanol, 1,3-thiazetidines were the main products.
Co-reporter:Nanyang Chen, Xiaoqing Meng, Fengjuan Zhu, Jiagao Cheng, Xusheng Shao, and Zhong Li
Journal of Agricultural and Food Chemistry 2015 Volume 63(Issue 5) pp:1360-1369
Publication Date(Web):January 22, 2015
DOI:10.1021/jf505281p
Tetraheterocyclic tetrahydroindeno[1′,2′:4,5]pyrrolo[1,2-a]imidazol-5(1H)-one derivatives as novel neonicotinoid candidates were designed and prepared by selective etherification, chlorination and esterification of ninhydrin-heterocyclic ketene aminals adducts. Some of the designed compounds showed excellent insecticidal activity against cowpea aphids (Aphis craccivora), brown planthopper (Nilaparvata lugens), and armyworm (Mythimna separata). In particular, the activity against armyworm (Mythimna separata) improved a lot in contrast with that of imidacloprid and cycloxaprid. The research here provides a novel neonicotinoid chemotype for further development.
Co-reporter:Fengjuan Zhu, Minming Zou, Xusheng Shao and Zhong Li
RSC Advances 2015 vol. 5(Issue 76) pp:61752-61758
Publication Date(Web):10 Jul 2015
DOI:10.1039/C5RA11213C
2-Aryl-1,3,4-oxadiazoles are important functional molecules in many research fields. A green synthetic method for preparation of 2-aryl-1,3,4-oxadiazoles was developed using hydrazides and highly reactive 1,1-dichloro-2-nitroethene. This eco-friendly protocol featured high yields, purification simplicity, water-based reaction medium, energy efficiency and no addition of catalysts.
Co-reporter:Fengjuan Zhu, Xue Tian, Xusheng Shao, Zhong Li
Tetrahedron Letters 2015 Volume 56(Issue 43) pp:5945-5949
Publication Date(Web):21 October 2015
DOI:10.1016/j.tetlet.2015.09.048
A green methodology was established for direct amidation of anilines using 1,1-dichloro-2-nitroethene. The new protocol provides convenient N-nitroacetylation for the anilines. This method was applicable to anilines include anthranilic acids, anthranilamides, phenylbenzohydrazides, diphenylamine, and 2-aminobenzenesulfonamide. The amidation process was accomplished in water and the products can be easily separated by filtration.
Co-reporter:Jiling Li;Xiaoyong Xu;Xusheng Shao;Zhong Li
Luminescence 2015 Volume 30( Issue 8) pp:1285-1289
Publication Date(Web):
DOI:10.1002/bio.2894
Abstract
A novel semi-rigid latent chromophore E1, containing an amide subunit activated by an adjacent semi-rigid intramolecular hydrogen-bonding (IHB) unit, was designed for the detection of fluoride ion by the ‘naked-eye’ in CH3CN. Comparative studies on structural analogs (E2, E3, and E4) provided significant insight into the structural and functional role of the amide N–H and IHB segment in the selective recognition of fluoride ions. The deprotonation of the amide N–H followed by the enhancement of intramolecular charge transfer (ICT) induced the colorimetric detection of E1 for fluoride ion. Copyright © 2015 John Wiley & Sons, Ltd.
Co-reporter:Nanyang Chen;Minming Zou;Xue Tian;Fengjuan Zhu;Danping Jiang;Jiagao Cheng;Xusheng Shao;Zhong Li
European Journal of Organic Chemistry 2014 Volume 2014( Issue 28) pp:6210-6218
Publication Date(Web):
DOI:10.1002/ejoc.201402677
Abstract
Ninhydrin and heterocyclic ketene aminals (HKAs) are versatile building blocks in organic chemistry. Reactions of ninhydrin with HKAs initially produced the kinetic products indeno[1,2-b]pyrrol-4(1H)-one derivatives, which could further isomerize to thermodynamic counterparts indeno[2,1-b]pyrrol-8(1H)-ones. The isomerization showed a strong solvent dependency and occurred through a decomposition–reconstruction pathway. This is the first example of isomerization of ninhydrin-constructed products. The conversion between kinetic and thermodynamic control may be applicable to similar reactions involving ninhydrin or HKAs.
Co-reporter:Nan-Yang Chen, Li-Ping Ren, Min-Ming Zou, Zhi-Ping Xu, Xu-Sheng Shao, Xiao-Yong Xu, Zhong Li
Chinese Chemical Letters 2014 Volume 25(Issue 2) pp:197-200
Publication Date(Web):February 2014
DOI:10.1016/j.cclet.2013.12.004
Spiro heterocycles frequently occur in bioactive molecules. In the pursuit of neonicotinoids with spiro heterocycles, three types of novel neonicotinoids with spirobenzofuranone, spirooxindole or spiroacenaphythylenone framework were designed and synthesized. Insecticidal evaluation showed that some of spirobenzofuranone containing neonicotinoids exhibited moderate activity against cowpea aphid, armyworm or brown planthopper.In the pursuit of neonicotinoids with spiro heterocycles, three types of novel neonicotinoids with spirobenzofuranone, spirooxindole or spiroacenaphythylenone framework were designed and synthesized.
Co-reporter:Min-Ming Zou, Feng-Juan Zhu, Xue Tian, Li-Ping Ren, Xu-Sheng Shao, Zhong Li
Chinese Chemical Letters 2014 Volume 25(Issue 12) pp:1515-1519
Publication Date(Web):December 2014
DOI:10.1016/j.cclet.2014.09.018
An efficient synthetic pathway to 2-oxo-1,2-dihydropyridine-fused 1,3-diaza heterocycles from heterocyclic ketene aminals, phathalic anhydride and ethyl cyanacetate was established. This protocol involved aza-ene reaction/imine-enamine tautomerization/enamine-ester exchange/ring-opening reaction sequence.An efficient synthetic pathway to 2-oxo-1,2-dihydropyridine-fused 1,3-diaza heterocycles from heterocyclic ketene aminals, phathalic anhydride and ethyl cyanacetate was established.
Co-reporter:Kathleen A. Durkin;Xusheng Shao;Shanshan Xia;John E. Casida
PNAS 2013 Volume 110 (Issue 43 ) pp:17273-17277
Publication Date(Web):2013-10-22
DOI:10.1073/pnas.1316369110
The nicotinic acetylcholine (ACh) receptor (nAChR) is the principal insecticide target. Nearly half of the insecticides by
number and world market value are neonicotinoids acting as nAChR agonists or organophosphorus (OP) and methylcarbamate (MC)
acetylcholinesterase (AChE) inhibitors. There was no previous evidence for in vivo interactions of the nAChR agonists and
AChE inhibitors. The nitromethyleneimidazole (NMI) analog of imidacloprid, a highly potent neonicotinoid, was used here as
a radioligand, uniquely allowing for direct measurements of house fly (Musca domestica) head nAChR in vivo interactions with various nicotinic agents. Nine neonicotinoids inhibited house fly brain nAChR [3H]NMI binding in vivo, corresponding to their in vitro potency and the poisoning signs or toxicity they produced in intrathoracically
treated house flies. Interestingly, nine topically applied OP or MC insecticides or analogs also gave similar results relative
to in vivo nAChR binding inhibition and toxicity, but now also correlating with in vivo brain AChE inhibition, indicating
that ACh is the ultimate OP- or MC-induced nAChR active agent. These findings on [3H]NMI binding in house fly brain membranes validate the nAChR in vivo target for the neonicotinoids, OPs and MCs. As an exception,
the remarkably potent OP neonicotinoid synergist, O-propyl O-(2-propynyl) phenylphosphonate, inhibited nAChR in vivo without the corresponding AChE inhibition, possibly via a reactive
ketene metabolite reacting with a critical nucleophile in the cytochrome P450 active site and the nAChR NMI binding site.
Co-reporter:Xusheng Shao;Xinglong Huang;Qian Shi;Zhong Li;Liming Tao ;Gonghua Song
Journal of Heterocyclic Chemistry 2012 Volume 49( Issue 5) pp:1136-1142
Publication Date(Web):
DOI:10.1002/jhet.969
The chlorothiazolyl moiety was an effective bioisoster of chloropyridyl in pesticide molecular design. Replacement of chloropyridyl in cis-nitromethylene neonicotinoids with chlorothiazolyl generated the chlorothiazolyl counterpart of nitromethylene neonicotinoids with tetrahydropyridine fixed cis-configuration. Bioassay against cowpea aphis (Aphis craccivora) indicated that the chlorothiazolyl analogs could maintain the high insecticidal activity.
Co-reporter:Xue Tian, Chao Zhang, Qi Xu, Zhong Li and Xusheng Shao
Organic & Biomolecular Chemistry 2017 - vol. 15(Issue 15) pp:NaN3323-3323
Publication Date(Web):2017/03/17
DOI:10.1039/C6OB02813F
Benzoylphenylureas (BPUs) are used as synthetic insect growth regulators for inhibiting chitin synthesis. Merging insecticidal BPUs with photoswitchable azobenzene generated photoresponsive chitin synthesis inhibitors. A prepared azobenzene-benzoylphenylurea can be activated upon irradiation with UV light, and shows 6-fold and 2-fold activity difference to armyworm (Mythimna separata) and German cockroach (Blattella germanica) sulfonylurea receptors, respectively. This is the first example of a photoswitchable BPU insecticide. The generation of such a photoresponsive BPU insecticide allows for modulation of the insecticidal activity by light, and may facilitate the spatiotemporal control over the sulfonylurea receptor and the mechanistic study of this kind of insecticide.