Co-reporter:Jiaqiong Sun, Guangfan Zheng, Qiao Zhang, Yimin Wang, Shengbiao Yang, Qian Zhang, Yan Li, and Qian Zhang
Organic Letters July 21, 2017 Volume 19(Issue 14) pp:3767-3767
Publication Date(Web):July 6, 2017
DOI:10.1021/acs.orglett.7b01599
The first copper-catalyzed imidovinylation of alkynes has been developed, which grants facile access to various (E)-2-imido-2,4-dienals with high stereoselectivity under mild conditions. This transformation also represents the first 1,3-carbon migration of propargylic alcohols and their derivatives.
Co-reporter:Qiao Zhang, Guangfan Zheng, Qian Zhang, Yan Li, and Qian Zhang
The Journal of Organic Chemistry August 4, 2017 Volume 82(Issue 15) pp:8258-8258
Publication Date(Web):July 18, 2017
DOI:10.1021/acs.joc.7b01089
The first metal-free, three-component radical aminofluorination of styrene derivatives has been developed, which employs Selectfluor as a fluorine source and azole derivatives as a nitrogen source. This transformation proceeds with high regioselectivity, providing various 1,2-aminofluorination compounds under mild conditions. Mechanistic studies suggest that the aminofluorination process might involve radical fluorination followed by nucleophilic amination.
Co-reporter:Yunhe Lv, Weiya Pu, Qian Chen, Qingqing Wang, Jiejie Niu, and Qian Zhang
The Journal of Organic Chemistry August 4, 2017 Volume 82(Issue 15) pp:8282-8282
Publication Date(Web):July 10, 2017
DOI:10.1021/acs.joc.7b01313
The copper-catalyzed highly regioselective aminodifluoroalkylation of alkynes and α-bromodifluoroacetamides was realized for the first time. With this method, 3,3-difluoro-1H-pyrrol-2(3H)-ones were constructed in a single step from various alkynes and α-bromodifluoroacetamides substrates without using any extra oxidant.
Co-reporter:Zhanyu Li, Jinbo Zhao, Baozhen Sun, Tingting Zhou, Mingzhu Liu, Shuang Liu, Mengru Zhang, and Qian Zhang
Journal of the American Chemical Society August 30, 2017 Volume 139(Issue 34) pp:11702-11702
Publication Date(Web):August 7, 2017
DOI:10.1021/jacs.7b06523
We report realization of the first enantioselective Cope-type hydroamination of oximes for asymmetric nitrone synthesis. The ligand promoted asymmetric cyclopropene “hydronitronylation” process employs a Cu-based catalytic system and readily available starting materials, operates under mild conditions and displays broad scope and exceptionally high enantio- and diastereocontrol. Preliminary mechanistic studies corroborate a CuI-catalytic profile featuring an olefin metalla-retro-Cope aminocupration process as the key C–N bond forming event. This conceptually novel reactivity enables the first example of highly enantioselective catalytic nitrone formation process and will likely spur further developments that may significantly expedite chiral nitrone synthesis.
Co-reporter:Yunhe Lv;Weiya Pu;Qingqing Wang;Qian Chen;Jiejie Niu
Advanced Synthesis & Catalysis 2017 Volume 359(Issue 18) pp:3114-3119
Publication Date(Web):2017/09/18
DOI:10.1002/adsc.201700559
AbstractCopper-catalyzed external-oxidant-free regioselective aminodifluoroalkylation of alkenes with readily available α-bromodifluoroacetamides was realized. This reaction exhibits good functional group tolerance with respect to alkenes and α-bromodifluoroacetamides in affording 3,3-difluoropyrrolidin-2-ones. A mechanism involving copper-catalyzed generation of a difluoroalkyl radical is proposed.
Co-reporter:Tony Wheellyam Pouambeka;Ge Zhang;Guang-Fan Zheng;Guo-Xing Xu;Tao Xiong
Organic Chemistry Frontiers 2017 vol. 4(Issue 7) pp:1420-1424
Publication Date(Web):2017/06/27
DOI:10.1039/C7QO00146K
The copper-catalyzed oxidative amidation of readily available α,β-unsaturated ketones with N-fluorobenzenesulfonimide (NFSI) for the synthesis of biologically active enamides or α-amino substituted unsaturated ketone skeletons has been achieved. These transformations processed via a radical pathway, thus the amidation occurred at the unusual α-position of the α,β-unsaturated ketones, leading to the following effective C(CO)–C(vinyl) or C(vinyl)–H bond cleavage with high selectivity.
Co-reporter:Yang Liu, Guangfan Zheng, Qian Zhang, Yan LiQian Zhang
The Journal of Organic Chemistry 2017 Volume 82(Issue 4) pp:
Publication Date(Web):January 26, 2017
DOI:10.1021/acs.joc.6b03049
A copper-catalyzed highly regio- and stereospecific selenosulfonation of alkynes with arylsulfonohydrazides and diphenyl diselenide has been developed. This novel three component reaction proceeds under very mild conditions and with a broad scope of substrates, providing a wide range of (E)-β-selenovinyl sulfones in good to excellent yields.
Co-reporter:Tao Xiong and Qian Zhang
Chemical Society Reviews 2016 vol. 45(Issue 11) pp:3069-3087
Publication Date(Web):27 Apr 2016
DOI:10.1039/C5CS00852B
The interesting and diverse biological activities of nitrogen-containing compounds make the construction of the C–N bond of great importance. Despite the tremendous advances that have been made in this research field, C–N bond formation based on nitrogen-centered radicals remains a significant challenge due to the harsh conditions required for the generation of nitrogen-centered radicals and their propensity for hydrogen abstraction or engaging in other degradation pathways. In the past several years, novel methodologies for C–N bond constructions based on nitrogen centered-radical intermediates, coordinated with metal or generated in the presence of visible-light and a photocatalyst, have attracted considerable attention. This tutorial review will summarize the significant progress of these efficient and mild radical amination reactions, with an emphasis on approaches for the generation of nitrogen-centered radicals and their reaction patterns, related mechanisms and synthetic applications, as well as unmet challenges in this emerging and promising field.
Co-reporter:Zhanyu Li, Guochun Peng, Jinbo Zhao, and Qian Zhang
Organic Letters 2016 Volume 18(Issue 19) pp:4840-4843
Publication Date(Web):September 22, 2016
DOI:10.1021/acs.orglett.6b02307
An efficient generation of functionalized allyl copper(I) species via cyclopropene ring-opening coupling reaction is reported, which enables stereoselective access to allylphosphonates. Mechanistic studies uncovered stereochemistry to be controlled by both ligand and substrate electronics, with the latter likely arising from pronounced arene-Cu(I) interaction in electron-deficient substrates. The study unravels a novel approach to access functionalized nucleophilic allylcopper species upon which three-component coupling reactions might be developed.
Co-reporter:Guangfan Zheng;Jinbo Zhao;Zhanyu Li;Qiao Zhang;Jiaqiong Sun;Haizhu Sun
Chemistry - A European Journal 2016 Volume 22( Issue 10) pp:3513-3518
Publication Date(Web):
DOI:10.1002/chem.201504534
Abstract
By using N-fluorobenzenesulfonimide as both the oxidant and the amination reagent, we have realized the first example of the intermolecular chalcogenative amination of alkynes, which grants facile, highly regio- and stereoselective access to chalcogenated enamides. The reaction features mild conditions, high yields and selectivities, remarkably broad substrate scope, and excellent functional group tolerance. Mechanistic studies indicate the in situ generated chalcogen imidates to be the actual reactive species, which in turn, has clarified the mechanism of related transformations. These reactions represent significant additions to the development of the highly selective amino bisfunctionalization of alkynes.
Co-reporter:Kai Sun;Yan Li
Science China Chemistry 2015 Volume 58( Issue 8) pp:1354-1358
Publication Date(Web):2015 August
DOI:10.1007/s11426-015-5385-y
A novel copper-catalyzed direct C-N formation reaction of simple arenes with cheap and pharmacological saccharin derivatives under relatively mild conditions was developed with arenes as limiting reagents. This work provided a new method for oxidative coupling of aromatic C(sp2)-H bonds and N-H bonds.
Co-reporter:Ge Zhang; Tao Xiong;Zining Wang;Guoxing Xu;Xuedan Wang ; Qian Zhang
Angewandte Chemie 2015 Volume 127( Issue 43) pp:12840-12844
Publication Date(Web):
DOI:10.1002/ange.201506066
Abstract
The first controllable, regioselective radical amination of allenes with N-fluoroarylsulfonimide is described to proceed under very mild reaction conditions. With this methodology, a general and straightforward route for the synthesis of both allenamides and fluorinated tetrasubstituted alkenes was realized from a wide range of terminal and internal allenes.
Co-reporter:Ge Zhang; Tao Xiong;Zining Wang;Guoxing Xu;Xuedan Wang ; Qian Zhang
Angewandte Chemie International Edition 2015 Volume 54( Issue 43) pp:12649-12653
Publication Date(Web):
DOI:10.1002/anie.201506066
Abstract
The first controllable, regioselective radical amination of allenes with N-fluoroarylsulfonimide is described to proceed under very mild reaction conditions. With this methodology, a general and straightforward route for the synthesis of both allenamides and fluorinated tetrasubstituted alkenes was realized from a wide range of terminal and internal allenes.
Co-reporter:Yunhe Lv, Yan Li, Tao Xiong, Yu Lu, Qun Liu and Qian Zhang
Chemical Communications 2014 vol. 50(Issue 18) pp:2367-2369
Publication Date(Web):09 Jan 2014
DOI:10.1039/C3CC48887J
nBu4NI-Catalyzed oxidative imidation of ketones and imides for the synthesis of α-amino ketones were realized for the first time. The methodology is characterized by its wide substrate scope even for acetone with readily available phthalimide, saccharin and succinimide, which opens a new pathway for direct imidation of ketones.
Co-reporter:Wei Yang, Jiaqiong Sun, Xianxiu Xu, Qian Zhang and Qun Liu
Chemical Communications 2014 vol. 50(Issue 34) pp:4420-4422
Publication Date(Web):13 Jan 2014
DOI:10.1039/C3CC49496A
A novel hydroamination of aryl C–H bonds has been accomplished using N-Boc-hydroxyamine via synergistic combination of rhodium and copper catalysis. The merger of two robust catalytic systems has allowed for the development of a mild and sustainable protocol for the direct formation of benzo[c]isoxazol-3(1H)-ones.
Co-reporter:Hongwei Zhang;Yongcheng Song;Dr. Jinbo Zhao; Jingping Zhang; Qian Zhang
Angewandte Chemie International Edition 2014 Volume 53( Issue 41) pp:11079-11083
Publication Date(Web):
DOI:10.1002/anie.201406797
Abstract
The copper-catalyzed radical aminofluorination of styrenes with N-fluorobenzenesulfonimide (NFSI) is realized with high regioselectivity, thus affording aminofluorination products with regioselectivities opposite that of the palladium-catalyzed and noncatalyzed processes. Preliminary mechanistic studies suggested the reaction went through a radical pathway and was supported by DFT calculations. In these reactions, NFSI is utilized as both a radical nitrogen source and radical fluorine source, thus rendering it an attractive reagent.
Co-reporter:Yunhe Lv, Yiying Zheng, Yan Li, Tao Xiong, Jingping Zhang, Qun Liu and Qian Zhang
Chemical Communications 2013 vol. 49(Issue 78) pp:8866-8868
Publication Date(Web):21 Aug 2013
DOI:10.1039/C3CC45084H
An unprecedented oxidant-mediated reductive amination of tertiary anilines and aldehydes without external reducing agents was developed via the nucleophilic attack of the oxygen atom of the carbonyl group to in situ generated iminium ions, in which tertiary anilines were used as both nitrogen source and reducing agent for the first time.
Co-reporter:Yunhe Lv, Yan Li, Tao Xiong, Weiya Pu, Hongwei Zhang, Kai Sun, Qun Liu and Qian Zhang
Chemical Communications 2013 vol. 49(Issue 57) pp:6439-6441
Publication Date(Web):30 May 2013
DOI:10.1039/C3CC43129K
An efficient Cu-catalyzed synthesis of quinazolines via the C–N bond formation reactions between N–H bonds of amidines and C(sp3)–H bonds adjacent to sulfur or nitrogen atoms in the commonly used solvents, such as DMSO, DMF, DMA, NMP or TMEDA, followed by intramolecular C–C bond formation reactions was developed for the first time.
Co-reporter:Yiying Zheng, Tao Xiong, Yunhe Lv, Jingping Zhang and Qian Zhang
Organic & Biomolecular Chemistry 2013 vol. 11(Issue 45) pp:7923-7930
Publication Date(Web):19 Sep 2013
DOI:10.1039/C3OB41299G
A combination of computational and experimental methods was carried out to elucidate the mechanism of palladium-catalyzed water-assisted benzylic C–H amination with N-fluorobenzenesulfonimide (NFSI), which involved the oxidative addition of PdII to PdIV-species as a rate-limiting step, followed by water-assisted concerted metalation–deprotonation (CMD) of the PdIV complex and water-assisted reductive elimination (RE) processes, and then a nucleophilic addition process to generate the final product and complete the catalytic cycle. The stability of the PdIV complex could be ascribed to the suitable ligands with strong σ-donors and resistance to decomposition, as well as being sufficiently bulky because the water-clusters assembled the ligands through hydrogen bonds to act as one multidentate ligand. Calculation results suggested that water also plays a crucial role as a proton transferring bridge in water-assisted CMD and RE processes. The corresponding experimental findings substantiate the expectation. Additionally, NFSI was found to act as both the oxidant and the nitrogen source to facilitate the reaction, while the steric effect of the bulky –N(SO2Ph)2 group contributed to circumventing the o-C–H amination. In this reaction, we investigated a novel spiro-cyclopalladation intermediate, formed by the reaction of the PdIV centre with pristine-carbon instead of ortho-carbon, which might be valuable for our understanding and further development of transition metal catalyzed C–H functionalization.
Co-reporter:Jianquan Liu;Zhongxue Fang; Qian Zhang; Qun Liu; Xihe Bi
Angewandte Chemie International Edition 2013 Volume 52( Issue 27) pp:6953-6957
Publication Date(Web):
DOI:10.1002/anie.201302024
Co-reporter:Hongwei Zhang;Weiya Pu;Dr. Tao Xiong;Dr. Yan Li;Xue Zhou;Kai Sun;Dr. Qun Liu ;Dr. Qian Zhang
Angewandte Chemie International Edition 2013 Volume 52( Issue 9) pp:2529-2533
Publication Date(Web):
DOI:10.1002/anie.201209142
Co-reporter:Lujia Mao, Yan Li, Tao Xiong, Kai Sun, and Qian Zhang
The Journal of Organic Chemistry 2013 Volume 78(Issue 2) pp:733-737
Publication Date(Web):December 13, 2012
DOI:10.1021/jo302144w
An efficient synthesis of tetramic acid derivatives was developed via intramolecular sp3 C–H aminations of 1-acetyl N-aryl cyclopropane/cyclopentanecarboxamides in the presence of PhI(OPiv)2 and CH3CH2COOH.
Co-reporter:Tao Xiong, Yan Li, Lujia Mao, Qian Zhang and Qian Zhang
Chemical Communications 2012 vol. 48(Issue 16) pp:2246-2248
Publication Date(Web):17 Jan 2012
DOI:10.1039/C2CC16720D
A new palladium-catalyzed highly regioselective allylic C–H amination of alkenes with NFSI in the presence of a catalytic amount of water was developed and successfully expanded to Selectfluor-mediated palladium-catalyzed aminations of alkenes with N-tosylcarbamates in water at room temperature.
Co-reporter:Yan Li, Zhongshu Li, Tao Xiong, Qian Zhang, and Xiangyang Zhang
Organic Letters 2012 Volume 14(Issue 13) pp:3522-3525
Publication Date(Web):June 22, 2012
DOI:10.1021/ol301492d
A novel Selectfluor-mediated copper-catalyzed highly selective benzylic C–O cyclization for the synthesis 4H-3,1-benzoxazines is reported. The predominant selectivity for a benzylic C(sp3)–H over an aromatic C(sp2)–H bond in N-o-tolylbenzamides is achieved.
Co-reporter:Zhikun Ni;Dr. Qian Zhang;Tao Xiong;Yiying Zheng;Yan Li;Hongwei Zhang;Dr. Jingping Zhang;Dr. Qun Liu
Angewandte Chemie International Edition 2012 Volume 51( Issue 5) pp:1244-1247
Publication Date(Web):
DOI:10.1002/anie.201107427
Co-reporter:Zhikun Ni;Dr. Qian Zhang;Tao Xiong;Yiying Zheng;Yan Li;Hongwei Zhang;Dr. Jingping Zhang;Dr. Qun Liu
Angewandte Chemie 2012 Volume 124( Issue 5) pp:1270-1273
Publication Date(Web):
DOI:10.1002/ange.201107427
Co-reporter:Kai Sun ; Yan Li ; Tao Xiong ; Jingping Zhang
Journal of the American Chemical Society 2011 Volume 133(Issue 6) pp:1694-1697
Publication Date(Web):January 20, 2011
DOI:10.1021/ja1101695
The first amide-directed, palladium-catalyzed, intermolecular, highly selective C−H aminations with the non-nitrene-based nitrogen source N-fluorobenzenesulfonimide have been developed. This methodology might provide a new pathway for directed metal-catalyzed aromatic C−H amination.
Co-reporter:Kai Wang, Xihe Bi, Shuangxi Xing, Peiqiu Liao, Zhongxue Fang, Xianyu Meng, Qian Zhang, Qun Liu and Yu Ji
Green Chemistry 2011 vol. 13(Issue 3) pp:562-565
Publication Date(Web):25 Jan 2011
DOI:10.1039/C0GC00848F
Cu2O as the catalyst in water was found to be quite robust for the azide-alkyne cycloaddition (AAC) reaction, which was verified by a wide variety of applicable azides and alkynes. Water was proved to play an essential role because of a significant rate acceleration compared with reactions using organic solvents and conducted under neat conditions. The high catalytic performance of Cu2O/H2O system was further argued by decreasing the catalyst loading to ppm levels.
Co-reporter:Yeming Wang, Xihe Bi, Dehua Li, Peiqiu Liao, Yidong Wang, Jin Yang, Qian Zhang and Qun Liu
Chemical Communications 2011 vol. 47(Issue 2) pp:809-811
Publication Date(Web):11 Nov 2010
DOI:10.1039/C0CC03802D
A highly efficient iron-catalyzed approach to polysubstituted pyrroles has been developed through the [4C+1N] cyclization of 4-acetylenic ketones with primary amines, leading to the synthesis of a variety of tetra- and fully-substituted pyrroles as well as fused pyrrole derivatives in good to excellent yields.
Co-reporter:Tao Xiong;Yan Li;Dr. Xihe Bi;Yunhe Lv ;Dr. Qian Zhang
Angewandte Chemie International Edition 2011 Volume 50( Issue 31) pp:7140-7143
Publication Date(Web):
DOI:10.1002/anie.201101391
Co-reporter:Tao Xiong, Yan Li, Yunhe Lv and Qian Zhang
Chemical Communications 2010 vol. 46(Issue 36) pp:6831-6833
Publication Date(Web):18 Aug 2010
DOI:10.1039/C0CC02175J
An unprecedented remote amide-directed palladium-catalyzed intermolecular highly selective benzylic C–H amination with N-fluorobenzenesulfonimide is developed, which represents the first direct benzylic C–H amination with a non-nitrene nitrogen source. This methodology provides a novel approach to circumvent the common ortho aromatic C–H selectivity in directed palladium catalyzed C–H functionalization.
Co-reporter:Zhiguo Zhang, Qian Zhang, Zhikun Ni and Qun Liu
Chemical Communications 2010 vol. 46(Issue 8) pp:1269-1271
Publication Date(Web):16 Jan 2010
DOI:10.1039/B917856B
A new strategy for highly diastereoselective synthesis of furo[3,2-b]-β-lactams and furo[3,2-b]-γ-lactams via a novel Ag(I)-mediated intramolecular 1,3-dipolar cycloaddition of oxo-N-propargylamides, is developed and the possible mechanism of these transformation is proposed.
Co-reporter:Zhiguo Zhang Dr. ;Shaoguang Sun Dr.;Tao Xiong;Qun Liu
Angewandte Chemie International Edition 2007 Volume 46(Issue 10) pp:
Publication Date(Web):19 JAN 2007
DOI:10.1002/anie.200604276
In one easy step, doubly activated cyclopropanes 1 can be transformed into furoquinoline derivatives 2 through a tandem ring-opening/recyclization reaction mediated by SnCl4⋅5 H2O. A variety of substrates 1 derived from cheap starting materials were converted into the corresponding furoquinolines in good to excellent yields with high chemo- and regioselectivity. R=H, Me, OMe, Cl, or aromatic group is naphthyl.
Co-reporter:Zhiguo Zhang Dr. ;Shaoguang Sun Dr.;Tao Xiong;Qun Liu
Angewandte Chemie 2007 Volume 119(Issue 10) pp:
Publication Date(Web):19 JAN 2007
DOI:10.1002/ange.200604276
Ein einziger einfacher Schritt – eine Tandem-Ringöffnung/Recyclisierung, vermittelt durch SnCl4⋅5 H2O – führt von doppelt aktivierten Cyclopropanen 1 zu Furochinolinderivaten 2. Mit billigen Ausgangsverbindungen wurde eine Vielzahl an Substraten 1 erhalten, die in guten bis ausgezeichneten Ausbeuten und mit hoher Chemo- und Regioselektivität die entsprechenden Furochinoline ergaben. R=H, Me, OMe, Cl oder Naphthyl als Arylrest.
Co-reporter:Qian ZHANG, Jiang-shan CHEN, Yan-xiang CHENG, Li-xiang WANG, Dong-ge MA, Xia-bin JING, Fo-song WANG
Chemical Research in Chinese Universities 2006 Volume 22(Issue 5) pp:647-650
Publication Date(Web):September 2006
DOI:10.1016/S1005-9040(06)60181-5
Co-reporter:Zhiguo Zhang, Qian Zhang, Zhikun Ni and Qun Liu
Chemical Communications 2010 - vol. 46(Issue 8) pp:NaN1271-1271
Publication Date(Web):2010/01/16
DOI:10.1039/B917856B
A new strategy for highly diastereoselective synthesis of furo[3,2-b]-β-lactams and furo[3,2-b]-γ-lactams via a novel Ag(I)-mediated intramolecular 1,3-dipolar cycloaddition of oxo-N-propargylamides, is developed and the possible mechanism of these transformation is proposed.
Co-reporter:Tao Xiong, Yan Li, Lujia Mao, Qian Zhang and Qian Zhang
Chemical Communications 2012 - vol. 48(Issue 16) pp:NaN2248-2248
Publication Date(Web):2012/01/17
DOI:10.1039/C2CC16720D
A new palladium-catalyzed highly regioselective allylic C–H amination of alkenes with NFSI in the presence of a catalytic amount of water was developed and successfully expanded to Selectfluor-mediated palladium-catalyzed aminations of alkenes with N-tosylcarbamates in water at room temperature.
Co-reporter:Yunhe Lv, Yiying Zheng, Yan Li, Tao Xiong, Jingping Zhang, Qun Liu and Qian Zhang
Chemical Communications 2013 - vol. 49(Issue 78) pp:NaN8868-8868
Publication Date(Web):2013/08/21
DOI:10.1039/C3CC45084H
An unprecedented oxidant-mediated reductive amination of tertiary anilines and aldehydes without external reducing agents was developed via the nucleophilic attack of the oxygen atom of the carbonyl group to in situ generated iminium ions, in which tertiary anilines were used as both nitrogen source and reducing agent for the first time.
Co-reporter:Yunhe Lv, Yan Li, Tao Xiong, Weiya Pu, Hongwei Zhang, Kai Sun, Qun Liu and Qian Zhang
Chemical Communications 2013 - vol. 49(Issue 57) pp:NaN6441-6441
Publication Date(Web):2013/05/30
DOI:10.1039/C3CC43129K
An efficient Cu-catalyzed synthesis of quinazolines via the C–N bond formation reactions between N–H bonds of amidines and C(sp3)–H bonds adjacent to sulfur or nitrogen atoms in the commonly used solvents, such as DMSO, DMF, DMA, NMP or TMEDA, followed by intramolecular C–C bond formation reactions was developed for the first time.
Co-reporter:Tony Wheellyam Pouambeka, Ge Zhang, Guang-Fan Zheng, Guo-Xing Xu, Qian Zhang, Tao Xiong and Qian Zhang
Inorganic Chemistry Frontiers 2017 - vol. 4(Issue 7) pp:
Publication Date(Web):
DOI:10.1039/C7QO00146K
Co-reporter:Wei Yang, Jiaqiong Sun, Xianxiu Xu, Qian Zhang and Qun Liu
Chemical Communications 2014 - vol. 50(Issue 34) pp:NaN4422-4422
Publication Date(Web):2014/01/13
DOI:10.1039/C3CC49496A
A novel hydroamination of aryl C–H bonds has been accomplished using N-Boc-hydroxyamine via synergistic combination of rhodium and copper catalysis. The merger of two robust catalytic systems has allowed for the development of a mild and sustainable protocol for the direct formation of benzo[c]isoxazol-3(1H)-ones.
Co-reporter:Yunhe Lv, Yan Li, Tao Xiong, Yu Lu, Qun Liu and Qian Zhang
Chemical Communications 2014 - vol. 50(Issue 18) pp:NaN2369-2369
Publication Date(Web):2014/01/09
DOI:10.1039/C3CC48887J
nBu4NI-Catalyzed oxidative imidation of ketones and imides for the synthesis of α-amino ketones were realized for the first time. The methodology is characterized by its wide substrate scope even for acetone with readily available phthalimide, saccharin and succinimide, which opens a new pathway for direct imidation of ketones.
Co-reporter:Yeming Wang, Xihe Bi, Dehua Li, Peiqiu Liao, Yidong Wang, Jin Yang, Qian Zhang and Qun Liu
Chemical Communications 2011 - vol. 47(Issue 2) pp:NaN811-811
Publication Date(Web):2010/11/11
DOI:10.1039/C0CC03802D
A highly efficient iron-catalyzed approach to polysubstituted pyrroles has been developed through the [4C+1N] cyclization of 4-acetylenic ketones with primary amines, leading to the synthesis of a variety of tetra- and fully-substituted pyrroles as well as fused pyrrole derivatives in good to excellent yields.
Co-reporter:Tao Xiong, Yan Li, Yunhe Lv and Qian Zhang
Chemical Communications 2010 - vol. 46(Issue 36) pp:NaN6833-6833
Publication Date(Web):2010/08/18
DOI:10.1039/C0CC02175J
An unprecedented remote amide-directed palladium-catalyzed intermolecular highly selective benzylic C–H amination with N-fluorobenzenesulfonimide is developed, which represents the first direct benzylic C–H amination with a non-nitrene nitrogen source. This methodology provides a novel approach to circumvent the common ortho aromatic C–H selectivity in directed palladium catalyzed C–H functionalization.
Co-reporter:Tao Xiong and Qian Zhang
Chemical Society Reviews 2016 - vol. 45(Issue 11) pp:NaN3087-3087
Publication Date(Web):2016/04/27
DOI:10.1039/C5CS00852B
The interesting and diverse biological activities of nitrogen-containing compounds make the construction of the C–N bond of great importance. Despite the tremendous advances that have been made in this research field, C–N bond formation based on nitrogen-centered radicals remains a significant challenge due to the harsh conditions required for the generation of nitrogen-centered radicals and their propensity for hydrogen abstraction or engaging in other degradation pathways. In the past several years, novel methodologies for C–N bond constructions based on nitrogen centered-radical intermediates, coordinated with metal or generated in the presence of visible-light and a photocatalyst, have attracted considerable attention. This tutorial review will summarize the significant progress of these efficient and mild radical amination reactions, with an emphasis on approaches for the generation of nitrogen-centered radicals and their reaction patterns, related mechanisms and synthetic applications, as well as unmet challenges in this emerging and promising field.
Co-reporter:Yiying Zheng, Tao Xiong, Yunhe Lv, Jingping Zhang and Qian Zhang
Organic & Biomolecular Chemistry 2013 - vol. 11(Issue 45) pp:NaN7930-7930
Publication Date(Web):2013/09/19
DOI:10.1039/C3OB41299G
A combination of computational and experimental methods was carried out to elucidate the mechanism of palladium-catalyzed water-assisted benzylic C–H amination with N-fluorobenzenesulfonimide (NFSI), which involved the oxidative addition of PdII to PdIV-species as a rate-limiting step, followed by water-assisted concerted metalation–deprotonation (CMD) of the PdIV complex and water-assisted reductive elimination (RE) processes, and then a nucleophilic addition process to generate the final product and complete the catalytic cycle. The stability of the PdIV complex could be ascribed to the suitable ligands with strong σ-donors and resistance to decomposition, as well as being sufficiently bulky because the water-clusters assembled the ligands through hydrogen bonds to act as one multidentate ligand. Calculation results suggested that water also plays a crucial role as a proton transferring bridge in water-assisted CMD and RE processes. The corresponding experimental findings substantiate the expectation. Additionally, NFSI was found to act as both the oxidant and the nitrogen source to facilitate the reaction, while the steric effect of the bulky –N(SO2Ph)2 group contributed to circumventing the o-C–H amination. In this reaction, we investigated a novel spiro-cyclopalladation intermediate, formed by the reaction of the PdIV centre with pristine-carbon instead of ortho-carbon, which might be valuable for our understanding and further development of transition metal catalyzed C–H functionalization.