Co-reporter:Huanfeng Jiang, Wentao Yu, Xiaodong Tang, Jianxiao Li, and Wanqing Wu
The Journal of Organic Chemistry September 15, 2017 Volume 82(Issue 18) pp:9312-9312
Publication Date(Web):August 16, 2017
DOI:10.1021/acs.joc.7b01122
A copper-catalyzed aerobic oxidative reaction between aromatics or heteroaromatics with KSCN is developed by using O2 as the oxidant. The combination of Cu(OTf)2, N,N,N′,N′-tetramethylethylenediamine (TMEDA) and BF3·Et2O provides an efficient catalytic system, affording substituted thiocyanation products and 2-aminobenzothiazoles in excellent yields. The reaction also possesses a good functional group tolerance for both strong electron-withdrawing and electron-donating groups.
Co-reporter:Yue Yu, Yang Chen, Wei Huang, Wanqing Wu, and Huanfeng Jiang
The Journal of Organic Chemistry September 15, 2017 Volume 82(Issue 18) pp:9479-9479
Publication Date(Web):August 23, 2017
DOI:10.1021/acs.joc.7b01496
N-Tosylhydrazones generated in situ from cyclic ketones smoothly underwent a [3 + 2] cycloaddition to afford saturated spirocyclic pyrazoles and further transformed to the fused analogues via a ring expansion in certain cases. An inexpensive and renewable resource, calcium carbide, was utilized as the carbon source in the ring expansion. The salient features of this reaction include widely available starting materials, convenient one-pot/two-step procedure, great efficiency, and high regioselectivity. Remarkably, this reaction underwent a [1,5]-sigmatropic rearrangement process, which was supported by deuterium-labeling experiments.
Co-reporter:Xu Wang, Wenfang Xiong, Yubing Huang, Jiayi Zhu, Qiong Hu, Wanqing Wu, and Huanfeng Jiang
Organic Letters November 3, 2017 Volume 19(Issue 21) pp:5818-5818
Publication Date(Web):October 24, 2017
DOI:10.1021/acs.orglett.7b02771
A new and versatile multicomponent domino strategy has been developed for the synthesis of a series of 1H-indene and phthalimide derivatives from simple and readily available starting materials. This process operating under mild conditions shows a broad substrate scope with moderate to excellent yields.
Co-reporter:Wei Guo;Jianhua Liao;Lianfeng Fan;Chuanle Zhu;Yanwei Ren;Zhenming Zhang;Jiawei Li;Huanfeng Jiang
Organic Letters March 3, 2017 Volume 19(Issue 5) pp:1008-1011
Publication Date(Web):February 13, 2017
DOI:10.1021/acs.orglett.6b03865
A palladium-catalyzed fluoroalkylative cyclization of olefins with readily available Rf–I reagents to afford the corresponding fluoroalkylated 2,3-dihydrobenzofuran and indolin derivatives with moderate to excellent yields is reported. This novel procedure provides an efficient method for the construction of Csp3–CF2 and C–O/N bonds in one step. A wide range of functional groups are tolerated. It is proposed that a radical/SET (single electron transfer) pathway proceeding via the fluoroalkyl radical may be involved in the catalytic cycle.
Co-reporter:Wanqing Wu, Songjian Yi, Wei Huang, Di Luo, and Huanfeng Jiang
Organic Letters June 2, 2017 Volume 19(Issue 11) pp:
Publication Date(Web):May 18, 2017
DOI:10.1021/acs.orglett.7b00980
A convenient protocol for the synthesis of sulfonylated benzofurans via Ag-catalyzed oxidative cyclization has been established. Chemically stable and easily available sodium sulfinates were used as the sulfonylation reagents and building block for the heterocycle construction. With this novel strategy, various benzofurans bearing dual functional groups could be obtained in good yields with high chemo- and regioselectivities under mild conditions.
Co-reporter:Yubing Huang, Yue Yu, Zhongzhi Zhu, Chuanle Zhu, Jinghe Cen, Xianwei Li, Wanqing Wu, and Huanfeng Jiang
The Journal of Organic Chemistry July 21, 2017 Volume 82(Issue 14) pp:7621-7621
Publication Date(Web):June 28, 2017
DOI:10.1021/acs.joc.7b00836
A novel protocol for the synthesis of α-aryl nitriles has been successfully achieved via a copper-catalyzed cyanation of N-tosylhydrazones employing thiocyanate as the source of cyanide. The features of this method include a convenient operation, readily available substrates, low-toxicity thiocyanate salts, and a broad substrate scope.
Co-reporter:Dongqing Liu, Wei Guo, Wanqing Wu, and Huanfeng Jiang
The Journal of Organic Chemistry December 15, 2017 Volume 82(Issue 24) pp:13609-13609
Publication Date(Web):November 21, 2017
DOI:10.1021/acs.joc.7b02113
A base-mediated three-component tandem reaction for the synthesis of multisubstituted pyrimidines from amidines, aryl alkynes, and aldehydes in a one-pot manner has been developed. Advantages of this transformation include being transition-metal-free, high efficiency, available starting materials, and being environmentally friendly.
Co-reporter:Wanqing Wu, Zhiming Lin, Chuanle Zhu, Pengquan Chen, Jiawei Li, and Huanfeng Jiang
The Journal of Organic Chemistry December 1, 2017 Volume 82(Issue 23) pp:12746-12746
Publication Date(Web):September 1, 2017
DOI:10.1021/acs.joc.7b01862
A novel one-step strategy for the synthesis of aminocyclopropanephosphonates containing adjacent quaternary-tetrasubstituted carbon centers under transition-metal-free catalysis via [3+2] cycloaddition process has been developed. A series of aminocyclopropanephosphonates with adjacent quaternary-tetrasubstituted carbon centers including spirocyclopropyl adducts were obtained in moderate to excellent yields under mild reaction conditions. This protocol would find the potential applications in biochemistry and medicinal chemistry.
Co-reporter:Jianwen Peng, Yang Gao, Chuanle Zhu, Bifu Liu, Yinglan Gao, Miao Hu, Wanqing Wu, and Huanfeng Jiang
The Journal of Organic Chemistry April 7, 2017 Volume 82(Issue 7) pp:3581-3581
Publication Date(Web):March 17, 2017
DOI:10.1021/acs.joc.7b00098
A novel approach for the synthesis of polysubstituted 3-amino pyrroles via palladium-catalyzed three-component tandem reaction was developed. The procedure constructs various polysubstituted 3-amino pyrroles with moderate to excellent yields under mild reaction conditions with assembly efficiency, readily available starting materials, and good functional group tolerance. Furthermore, this process was successfully applied to the synthesis of different 3-phenyl-1,4-dihydropyrrolo[3,2-b]indole derivatives via an intramolecular Buchwald–Hartwig cross-coupling reaction in two steps.
Co-reporter:Lu Ouyang;Jiuzhong Huang;Jianxiao Li;Chaorong Qi;Huanfeng Jiang
Chemical Communications 2017 vol. 53(Issue 75) pp:10422-10425
Publication Date(Web):2017/09/19
DOI:10.1039/C7CC06077G
A novel Pd-catalyzed intermolecular cascade oxidative amination of homoallylic alcohols to yield β-amino ketones has been developed by using TBHP as the terminal oxidant. The synthetic utility of the reaction can be performed by installing the carbonyl and amino groups along an alkyl chain in one step, offering several advantages such as simple starting materials and easy operation. The resultant β-amino ketones should have potential applications in the fields of biopharmaceutical and functional materials.
Co-reporter:Yue Yu;Yang Chen;Huanfeng Jiang
Chemical Communications 2017 vol. 53(Issue 3) pp:640-643
Publication Date(Web):2017/01/03
DOI:10.1039/C6CC08320J
We have developed a Michael-addition/cyclization procedure between ene–yne–ketones and TMSCN under metal-free conditions. A wide range of cyanofurans was delivered in high yields, which could be further transformed to a series of furo-furanimines, furo-pyridazines or carboxamido-furans. In addition, deuterium-labeling experiments have been conducted to clarify the reaction pathway.
Co-reporter:Pengquan Chen;Chuanle Zhu;Rui Zhu;Zhiming Lin;Huanfeng Jiang
Organic & Biomolecular Chemistry 2017 vol. 15(Issue 5) pp:1228-1235
Publication Date(Web):2017/02/01
DOI:10.1039/C6OB02137A
A palladium-catalyzed cyclopropanation of internal alkenes with N-tosylhydrazones is presented. This gram-scale cyclopropanation reaction of maleimides provides a wide spectrum of 3-azabicyclo[3.1.0]hexane derivatives in high yields and diastereoselectivities. The major diastereoisomers could be easily isolated by chromatography on silica gel. This protocol provides a practical route to the mu opioid receptor antagonist CP-866,087.
Co-reporter:Xu Wang, Yubing Huang, Yanli Xu, Xiaodong Tang, Wanqing Wu, and Huanfeng Jiang
The Journal of Organic Chemistry 2017 Volume 82(Issue 4) pp:
Publication Date(Web):January 20, 2017
DOI:10.1021/acs.joc.6b02697
An efficient and simple palladium-catalyzed approach for the synthesis of aryl ketones from low-cost nitriles and arylhydrazines using molecular oxygen (O2) as sole oxidant via C–N bond cleavage is reported. Various aryl ketones were synthesized in moderate to good yields under mild conditions. A possible mechanism involving the PdII/Pd0 catalytic cycle process is depicted, and a cationic palladium intermediate was detected by ESI-MS.
Co-reporter:Jianxiao Li;Weigao Hu;Chunsheng Li;Shaorong Yang;Huanfeng Jiang
Organic Chemistry Frontiers 2017 vol. 4(Issue 3) pp:373-376
Publication Date(Web):2017/02/28
DOI:10.1039/C6QO00633G
A novel and efficient palladium-catalyzed aerobic cascade reaction of haloalkynes with unactivated alkenes for synthesis of functionalized oxetanes has been demonstrated. This cascade protocol, including chloropalladation and a Heck-like process, proceeds smoothly with good functional group tolerance and high selectivity.
Co-reporter:Zun Li;Jia Zheng;Weigao Hu;Jianxiao Li;Huanfeng Jiang
Organic Chemistry Frontiers 2017 vol. 4(Issue 7) pp:1363-1366
Publication Date(Web):2017/06/27
DOI:10.1039/C7QO00082K
Herein we describe a novel protocol for the rapid assembly of 1,4-enyne-3-ones from isocyanides and 1,6-enyne. During this process, two different types of C–C bonds were formed on the same isocyanide carbon atom via sequential decarboxylation, insertion of isocyanide, and reductive elimination. Moreover, this approach shows advantages of mild reaction conditions and excellent functional group compatibility.
Co-reporter:Wei Guo;Dongqing Liu;Jianhua Liao;Fanghua Ji;Huanfeng Jiang
Organic Chemistry Frontiers 2017 vol. 4(Issue 6) pp:1107-1111
Publication Date(Web):2017/05/31
DOI:10.1039/C6QO00842A
A facile and efficient approach for the synthesis of various pyrimidine derivatives from amidines and ketones via a Cu-catalyzed intermolecular oxidative coupling process using TEMPO/O2 as a co-oxidant has been developed. This novel protocol features unreactive C(sp3)–H bond amination, a wide range of substrates, good functional group tolerance and mild reaction conditions.
Co-reporter:Yubing Huang;Xianwei Li;Xu Wang;Yue Yu;Jia Zheng;Huanfeng Jiang
Chemical Science (2010-Present) 2017 vol. 8(Issue 10) pp:7047-7051
Publication Date(Web):2017/09/25
DOI:10.1039/C7SC02867A
Sulfur-containing nitriles have important research value in the life sciences due to their diverse biological activities resulting from the sulfur and cyano functional groups. Herein, a copper-catalyzed cyanothiolation of N-tosylhydrazones with thiocyanates to generate α-arylthioalkanenitriles bearing sulfur-substituted quaternary carbon center atoms has been described. This novel protocol involves the procedure of copper carbene species promoting S–CN bond cleavage and C–CN/C–S bond reconstruction to introduce both sulfur and cyano groups onto a single carbon center. This cyanothiolation reaction will greatly enhance the synthetic utility of carbenoid species as new entries for the construction of diverse heteroatom-containing nitriles via cyanofunctionalization of metal–carbene species.
Co-reporter:Jianxiao Li;Can Li;Lu Ouyang;Chunsheng Li;Huanfeng Jiang
Organic & Biomolecular Chemistry 2017 vol. 15(Issue 37) pp:7898-7908
Publication Date(Web):2017/09/26
DOI:10.1039/C7OB01889D
A straightforward and highly effective N-heterocyclic carbene-palladium catalyzed cascade annulation/alkynylation of 2-alkynylanilines with terminal alkynes has been enabled to afford free (NH)-3-alkynylindole derivatives in moderate to good yields. This protocol features mild conditions, broad substrate scope, and high atom- and step-economy. Notably, the resultant 3-alkynylindoles could be conveniently transformed into a variety of functionalized indole scaffolds, thus illustrating their potential applications in synthetic and pharmaceutical chemistry.
Co-reporter:Chuanle Zhu;Pengquan Chen;Rui Zhu;Zhiming Lin;Huanfeng Jiang
Chemical Communications 2017 vol. 53(Issue 18) pp:2697-2700
Publication Date(Web):2017/02/28
DOI:10.1039/C6CC10187A
A new example of CN double bond formation in metal carbene insertion reactions is reported. Remarkably, the general 1,2-migration process of the corresponding ylide intermediates in X–H carbene insertion reactions that leads to C–X single bond formation is completely inhibited by replacing the H atom with a nitrogen atom. This palladium-catalyzed carbene insertion reaction with NN double bonds gave various N,N-disubstituted hydrazone products in high yields.
Co-reporter:Wanqing Wu;Yanni An;Jianxiao Li;Shaorong Yang;Zhongzhi Zhu;Huanfeng Jiang
Organic Chemistry Frontiers 2017 vol. 4(Issue 9) pp:1751-1756
Publication Date(Web):2017/08/22
DOI:10.1039/C7QO00326A
An efficient and versatile iodine-catalyzed electrophilic cyclization has been achieved to afford functionalized 3-sulfenylcoumarin and 3-sulfenylquinolinone derivatives in moderate to good yields from readily available alkynes with sodium arylsulfinates. Moreover, broad substrate scope, excellent functional group compatibility, and high-value products make this protocol practical and attractive, offering potential applications in organic synthesis and medicinal chemistry.
Co-reporter:Jianxiao Li;Yanni An;Jiawei Li;Shaorong Yang;Huanfeng Jiang
Organic Chemistry Frontiers 2017 vol. 4(Issue 8) pp:1590-1594
Publication Date(Web):2017/07/26
DOI:10.1039/C7QO00215G
A novel and efficient palladium-catalyzed approach for copper-mediated C–S bond activation and functionalization of 3-sulfenylheteroarenes has been established. This protocol features good functional group compatibility and a broad substrate scope, and can serve as a powerful synthetic tool for the construction and late-stage modification of important heteroarene scaffolds. Remarkably, both the N-protected and free N–H indoles were nicely suitable for this transformation.
Co-reporter:Huanfeng Jiang;Wei Huang;Yue Yu;Songjian Yi;Jiawei Li
Chemical Communications 2017 vol. 53(Issue 54) pp:7473-7476
Publication Date(Web):2017/07/04
DOI:10.1039/C7CC03125D
We have developed a transition-metal free trifluoromethylation protocol between enamines and CF3SO2Na. A wide range of β-trifluoromethyl substituted enamines were delivered in moderate to high yields with only E-configurations.
Co-reporter:Lu Ouyang, Wanqing Wu
Current Opinion in Green and Sustainable Chemistry 2017 Volume 7(Volume 7) pp:
Publication Date(Web):1 October 2017
DOI:10.1016/j.cogsc.2017.07.005
Oxidation reactions have significant value in organic chemistry, having been in focus continuously due to the high efficiency in building up molecular complexity. In the past few decades, transition metal-catalyzed oxidation reactions have been significantly explored and have played important roles in organic synthesis. Compared to the widely-used oxidants, such as inorganic salts, peroxides, hypervalent iodine reagents and quinones, molecular oxygen (O2), which is natural, inexpensive, and environmentally friendly, is a highly appealing oxidant in academic and industry area for green and sustainable chemistry. Recently, significant advances have been made in palladium-catalyzed reactions using O2 as the oxidant. This critical review highlights some of the recent developments in molecular oxygen-involved Pd-catalyzed oxidation reactions with a focus on mechanistic strategies and new reaction developments.
Co-reporter:Chuanle Zhu;Rui Zhu;Pengquan Chen;Fulin Chen;Huanfeng Jiang
Advanced Synthesis & Catalysis 2017 Volume 359(Issue 18) pp:3154-3159
Publication Date(Web):2017/09/18
DOI:10.1002/adsc.201700336
AbstractThe first example for the generation of carbonyl ylides from palladium carbenes is reported. Systematic investigation of the substituents attached to the carbonyl group indicates that the employment of trifluoromethyl group as the substituent is very critical for the success of this transformation. The remarkable fluorine effect on the reactivity is very impressive, which allows the construction of various trifluoromethylated oxiranes in high yields and diastereoselectivities.
Co-reporter:Lu Ouyang;Jianxiao Li;Jia Zheng;Jiuzhong Huang;Chaorong Qi; Dr. Wanqing Wu; Dr. Huanfeng Jiang
Angewandte Chemie 2017 Volume 129(Issue 50) pp:16142-16146
Publication Date(Web):2017/12/11
DOI:10.1002/ange.201709285
AbstractA novel and convenient palladium catalytic system for the synthesis of α-amino acid esters from simple starting materials is reported. Hydrogen peroxide not only acts as the green oxidant, but also as the oxygen source. This strategy for the conversion of amines and vinyl ethers into highly functionalized and structurally diverse α-amino acid esters is characterized by the simplicity of the experimental procedure, mild reaction conditions, high atom economy, scalability, and practicability.
Co-reporter:Wanqing Wu, Songjian Yi, Yue Yu, Wei Huang, and Huanfeng Jiang
The Journal of Organic Chemistry 2017 Volume 82(Issue 2) pp:
Publication Date(Web):December 28, 2016
DOI:10.1021/acs.joc.6b02416
A novel strategy for the synthesis of sulfonylated lactones via Ag-catalyzed radical addition/cyclization reaction of 1,6-enynes and sodium sulfinates has been developed. The reaction presents high stereoselectivity under mild conditions with C4 prochiral center construction in one step. The ESR experiments and relevant mechanistic studies indicated that a radical pathway should be involved in this transformation.
Co-reporter:Jia Zheng, Zun Li, Liangbin Huang, Wanqing Wu, Jianxiao Li, and Huanfeng Jiang
Organic Letters 2016 Volume 18(Issue 15) pp:3514-3517
Publication Date(Web):July 15, 2016
DOI:10.1021/acs.orglett.6b01008
A new approach to construct 2,3-disubstituted quinolines is described via Pd-catalyzed oxidative cyclization of o-vinylanilines and alkynes with molecular oxygen. This transformation is supposed to undergo intermolecular amination of alkyne, insertion of the olefin, and oxidative cleavage of C–C bond sequence.
Co-reporter:Chuanle Zhu, Jiawei Li, Pengquan Chen, Wanqing Wu, Yanwei Ren, and Huanfeng Jiang
Organic Letters 2016 Volume 18(Issue 6) pp:1470-1473
Publication Date(Web):March 9, 2016
DOI:10.1021/acs.orglett.6b00416
Cyclopropanation of 2-aminoacrylates with N-tosylhydrazones could proceed smoothly under transition-metal-free conditions via a [3 + 2] cycloaddition process. This robust protocol exhibits excellent generality, delivering a wide spectrum of cyclopropane α-amino acid esters bearing contiguous quaternary carbon centers in high yields and diastereoselectivities. With these readily available products, the steric convergence of cyclopropane α-amino acids could be readily obtained.
Co-reporter:Yinglan Gao, Yang Gao, Xiaodong Tang, Jianwen Peng, Miao Hu, Wanqing Wu, and Huanfeng Jiang
Organic Letters 2016 Volume 18(Issue 5) pp:1158-1161
Publication Date(Web):February 25, 2016
DOI:10.1021/acs.orglett.6b00272
A new copper-catalyzed oxysulfenylation reaction of enolates with sodium sulfinates has been disclosed. A series of sulfenylated heterocycles including four- and seven-membered cyclic ether were obtained in mild to good yields. This reaction is proposed to go through a radical process, and the sulfur radical (RS•) may be a reactive species.
Co-reporter:Yue Yu, Songjian Yi, Chuanle Zhu, Weigao Hu, Bingjie Gao, Yang Chen, Wanqing Wu, and Huanfeng Jiang
Organic Letters 2016 Volume 18(Issue 3) pp:400-403
Publication Date(Web):January 13, 2016
DOI:10.1021/acs.orglett.5b03415
Under copper-catalyzed or base-promoted conditions, a wide range of ene-yne-ketones react with H-phosphonates to afford various phosphorylated furans in good yields. A copper carbene generation or a Michael addition is proposed as the key step in the selective construction of the Csp3–P or Csp2–P bond, which is supported by carbene capture reactions and interval 31P NMR experiments. Furthermore, this method features inexpensive metal catalysts, no usage of oxidant, and high atom economy, which make it attractive and practical.
Co-reporter:Jianwen Peng, Yang Gao, Weigao Hu, Yinglan Gao, Miao Hu, Wanqing Wu, Yanwei Ren, and Huanfeng Jiang
Organic Letters 2016 Volume 18(Issue 22) pp:5924-5927
Publication Date(Web):November 10, 2016
DOI:10.1021/acs.orglett.6b02999
A palladium-catalyzed multicomponent reaction (MCR) of propargylic carbonates with isocyanides is reported. Remarkably, the orderly insertion of isocyanides affords two types of valuable N-heterocyclic products (Z)-6-imino-4,6-dihydro-1H-furo[3,4-b]pyrrol-2-amines and (E)-5-iminopyrrolones in high yields. Systematic analysis of the reaction conditions indicates that the selectivity of these N-heterocyclic products can be controlled by ligands and temperature.
Co-reporter:Jia Zheng, Zun Li, Wanqing Wu, and Huanfeng Jiang
Organic Letters 2016 Volume 18(Issue 24) pp:6232-6235
Publication Date(Web):November 30, 2016
DOI:10.1021/acs.orglett.6b02710
The vinyl moiety-assisted selective O-nucleopalladation is reported, which offers rapid constructions of cycloolefins and cyclopropanes via oxidant-induced cyclization of enynes. O2 resulted in the unexpected 6-endo-Heck cyclization, while CuCl2 led to a 5-exo-trig pathway and synergetic SN2-type C–C bond formation. Amide works as an O-transferred nucleophilic group to activate the alkyne moiety, which induced divergent annulation processes. Moreover, the regenerated amides could be used for further modifications.
Co-reporter:Chuanle Zhu, Pengquan Chen, Wanqing Wu, Chaorong Qi, Yanwei Ren, and Huanfeng Jiang
Organic Letters 2016 Volume 18(Issue 16) pp:4008-4011
Publication Date(Web):August 9, 2016
DOI:10.1021/acs.orglett.6b01824
The first example of the epoxidation reaction of trifluoromethylketones with N-tosylhydrazones under transition-metal free conditions is reported. This epoxidation reaction provided tetrasubstituted trifluoromethylated oxiranes with excellent yields and diastereoselectivities. The salient features of this reaction include readily available starting materials, mild conditions, broad substrate scope, high efficiency, and valuable further applications. Remarkably, this reaction proceeded through an unprecedented nucleophilic addition process, and the ammonium O-anion intermediate was detected and characterized by NMR and HRMS analysis.
Co-reporter:Yubing Huang, Xianwei Li, Yue Yu, Chuanle Zhu, Wanqing Wu, and Huanfeng Jiang
The Journal of Organic Chemistry 2016 Volume 81(Issue 12) pp:5014-5020
Publication Date(Web):May 26, 2016
DOI:10.1021/acs.joc.6b00568
The first attempt at utilizing N-tosylhydrazones as two-carbon synthons has been successfully achieved, which underwent a copper-mediated [3 + 2] oxidative cyclization reaction to afford 2,3,5-trisubstituted furans in moderate to good yields. The features of this method include inexpensive metal catalyst, readily available substrates, high regioselectivity, and convenient operation. The studies provide important approaches for further exploration of the powerful and diverse reaction abilities of N-tosylhydrazones.
Co-reporter:Wei Guo, Chunsheng Li, Jianhua Liao, Fanghua Ji, Dongqing Liu, Wanqing Wu, and Huanfeng Jiang
The Journal of Organic Chemistry 2016 Volume 81(Issue 13) pp:5538-5546
Publication Date(Web):June 8, 2016
DOI:10.1021/acs.joc.6b00867
Various polysubstituted pyrimidines are smoothly formed via a base-promoted intermolecular oxidation C–N bond formation of allylic C(sp3)–H and vinylic C(sp2)–H of allyllic compounds with amidines using O2 as the sole oxidant. This protocol features protecting group free nitrogen sources, good functional group tolerance, high atom economy, and environmental advantages.
Co-reporter:Jianhua Liao, Wei Guo, Zhenming Zhang, Xiaodong Tang, Wanqing Wu, and Huanfeng Jiang
The Journal of Organic Chemistry 2016 Volume 81(Issue 3) pp:1304-1309
Publication Date(Web):January 12, 2016
DOI:10.1021/acs.joc.5b02674
An efficient procedure for the preparation of allylic trifluoromethanesulfones with high regioselectivity from aromatic allylic alcohols/esters and NaSO2CF3 under transition-metal-free conditions is described. A wide range of functional groups were tolerated. This is the first example to realize different types of allylic alcohols, including primary, secondary, and tertiary allylic alcohols, all of which transferred to the corresponding products efficiently in good to excellent yields with readily available and inexpensive NaSO2CF3. The synthetic utility of the method was demonstrated by performing the reaction at gram scale.
Co-reporter:Jianxiao Li, Chunsheng Li, Shaorong Yang, Yanni An, Wanqing Wu, and Huanfeng Jiang
The Journal of Organic Chemistry 2016 Volume 81(Issue 17) pp:7771-7783
Publication Date(Web):August 8, 2016
DOI:10.1021/acs.joc.6b01428
An efficient and convenient palladium-catalyzed C–H bond oxidative sulfenylation of indoles and related electron-rich heteroarenes with aryl boronic acids and elemental sulfur has been described. This procedure provides a useful and direct approach for the assembly of a wide range of structurally diverse 3-sulfenylheteroarenes with moderate to excellent yields from simple and readily available starting materials. Moreover, this synthetic protocol is suitable for N-protected and unprotected indoles. Notably, the construction of two C–S bonds in one step was also achieved in this transformation.
Co-reporter:Chunsheng Li, Jianxiao Li, Yanni An, Jianwen Peng, Wanqing Wu, and Huanfeng Jiang
The Journal of Organic Chemistry 2016 Volume 81(Issue 24) pp:12189-12196
Publication Date(Web):October 28, 2016
DOI:10.1021/acs.joc.6b01909
An efficient and practical palladium-catalyzed aerobic oxidative approach to afford functionalized 2-substituted quinolines in moderate to good yields from readily available allylbenzenes with aniline is developed. The present annulation process has high functional-group tolerance and high atom economy, making it a valuable and practical method in synthetic and medicinal chemistry. Moreover, this transformation is supposed to proceed through oxidation of allylic C–H functionalization to form C–C and C–N bonds in one pot.
Co-reporter:Jianxiao Li, Chunsheng Li, Shaorong Yang, Yanni An, Wanqing Wu, and Huanfeng Jiang
The Journal of Organic Chemistry 2016 Volume 81(Issue 7) pp:2875-2887
Publication Date(Web):March 15, 2016
DOI:10.1021/acs.joc.6b00162
A novel and efficient palladium-catalyzed cascade annulation/arylthiolation reaction has been developed to afford functionalized 3-sulfenylbenzofuran and 3-sulfenylindole derivatives in moderate to good yields from readily available 2-alkynylphenols and 2-alkynylamines in ionic liquids. This protocol provides a valuable synthetic tool for the assembly of a wide range of 3-sulfenylbenzofuran and 3-sulfenylindole derivatives with high atom- and step-economy and exceptional functional group tolerance. Moreover, the employment of ionic liquids under mild reaction conditions makes this transformation green and practical. Furthermore, this approach enriched current C–S bond formation chemistry, making a valuable and practical method in synthetic and medicinal chemistry.
Co-reporter:Huawen Huang, Wei Guo, Wanqing Wu, Chao-Jun Li, and Huanfeng Jiang
Organic Letters 2015 Volume 17(Issue 12) pp:2894-2897
Publication Date(Web):May 29, 2015
DOI:10.1021/acs.orglett.5b00995
A facile and versatile catalytic system involving copper catalyst, K3PO4 as the base, and O2 as the oxidant has been developed to enable efficient synthesis of 2,4,6-trisubstituted and 2,6-disubstituted 1,3,5-triazines and 1,3-disubstituted 1,2,4-triazoles from amidines with trialkylamines, DMSO, and DMF as the reaction partners, respectively. This protocol features inexpensive metal catalyst, green oxidant, good functional group tolerance, and high regioselectivity, providing an efficient entry to those products that are challenging to prepare by traditional methods. A single-electron-transfer (SET) mechanism is proposed for these transformations.
Co-reporter:Jianhua Liao, Zhenming Zhang, Xiaodong Tang, Wanqing Wu, Wei Guo, and Huanfeng Jiang
The Journal of Organic Chemistry 2015 Volume 80(Issue 17) pp:8903-8909
Publication Date(Web):August 18, 2015
DOI:10.1021/acs.joc.5b01463
An efficient palladium-catalyzed desulfitative oxidative coupling of sodium arylsulfinites for highly region-selective Heck-type reaction of allylic alcohols has been developed. The compatibility of the functionalities of −I, −Br, and −F would explore further postfunctionalization of the C–X bonds. This method provides a new and straightforward protocol for the synthesis of β-aryl ketones and aldehydes. The deuterium labeling experiments indicated that this transformation may proceed via a [1, 2-H] shift process.
Co-reporter:Zhenming Zhang, Lihuan Wu, Jianhua Liao, Wanqing Wu, Huanfeng Jiang, Jianxiao Li, and Jiawei Li
The Journal of Organic Chemistry 2015 Volume 80(Issue 15) pp:7594-7603
Publication Date(Web):July 14, 2015
DOI:10.1021/acs.joc.5b01178
Herein, an amide oxygen-assisted palladium-catalyzed hydration reaction of alkynes is realized to prepare a series of o-acylacetanilide derivatives with high yield, and single regioselectivity under mild reaction conditions. This transformation is simple, practical, and can be performed on a gram scale. Evaluation of the mechanism shows that the reaction should involve an oxypalladation process, and the 1,3-oxazine compound is proven to be a key intermediate.
Co-reporter:Yang Gao, Wenfang Xiong, Huoji Chen, Wanqing Wu, Jianwen Peng, Yinglan Gao, and Huanfeng Jiang
The Journal of Organic Chemistry 2015 Volume 80(Issue 15) pp:7456-7467
Publication Date(Web):July 9, 2015
DOI:10.1021/acs.joc.5b01024
A highly regio- and stereoselective C–C double bond formation reaction via Pd-catalyzed Heck-type cascade process with N-tosylhydrazones has been developed. Various N-tosylhydrazones derived from both ketones and aldehydes are found to be efficient substrates to provide di- and trisubstituted olefins with high regio- and stereoselectivity. Furthermore, this reaction has a good functional group tolerance and different benzofuran-, dihydrobenzofuran-, and indoline-containing alkene products were obtained with high selectivity.
Co-reporter:Zhenming Zhang;Dr. Wanqing Wu;Jianhua Liao;Jianxiao Li;Dr. Huanfeng Jiang
Chemistry - A European Journal 2015 Volume 21( Issue 18) pp:6708-6712
Publication Date(Web):
DOI:10.1002/chem.201500397
Abstract
Herein, the first example of chloropalladation-initiated asymmetric intermolecular carboesterification of alkenes with alkynes by using chiral amine auxiliaries is reported. The use of (1S,2S)-N1,N1-dimethylcyclohexane-1,2-diamine auxiliaries is essential for providing α-methylene-γ-lactones products in moderate to high yields and excellent enantioselectivities at room temperature. Moreover, the chiral amine auxiliaries can be readily removed by hydrolysis during the reaction process to keep the absolute configuration. This oxygen- and water-promoted asymmetric reaction opens a new window to study asymmetric processes in halopalladation reactions.
Co-reporter:Yang Gao, Wanqing Wu, Huawen Huang, Yubing Huang and Huanfeng Jiang
Chemical Communications 2014 vol. 50(Issue 7) pp:846-848
Publication Date(Web):31 Oct 2013
DOI:10.1039/C3CC47310D
A novel and efficient Pd-catalyzed intermolecular [3 + 2] carbocyclization of alkynols and electron-deficient alkynes for the synthesis of halo-cyclopentadienes (Cps) has been developed. The present protocol employs simple propargyl alcohols as the C3 group to participate in the cyclization reaction, providing a highly convenient and atom-economical entry to the halo-cyclopentadiene framework.
Co-reporter:Yang Gao, Yubing Huang, Wanqing Wu, Kefan Huang and Huanfeng Jiang
Chemical Communications 2014 vol. 50(Issue 61) pp:8370-8373
Publication Date(Web):18 Jun 2014
DOI:10.1039/C4CC03062A
An efficient Pd-catalyzed oxidative cyclization reaction for the synthesis of functionalized indolines by direct C–H activation of acetanilide has been developed. The norbornylpalladium species formed via direct ortho C–H activation of acetanilides is supposed to be a key intermediate in this transformation.
Co-reporter:Zhenming Zhang, Lu Ouyang, Wanqing Wu, Jianxiao Li, Zhicai Zhang, and Huanfeng Jiang
The Journal of Organic Chemistry 2014 Volume 79(Issue 22) pp:10734-10742
Publication Date(Web):September 12, 2014
DOI:10.1021/jo501606c
A novel chloropalladation-initiated intermolecular oxyvinylcyclization of alkenes with alkynoic acids or alkynols is developed. This protocol provides a series of 3-methylene γ-lactone and tetrahydrofuran derivatives in moderate to excellent yields with high stereoselectivities in the presence of PdCl2 and CuCl2 or CuCl2·2H2O. Besides a broad substrate scope, this method has the advantages of mild reaction conditions and easily accessible starting materials. Furthermore, the construction of C–Cl, C(sp2)–C(sp3), and C–O bonds in one step was also achieved in this transformation.
Co-reporter:Yang Gao;Meizhou Yin;Huawen Huang ;Huanfeng Jiang
Advanced Synthesis & Catalysis 2013 Volume 355( Issue 11-12) pp:2263-2273
Publication Date(Web):
DOI:10.1002/adsc.201300157
Co-reporter:Yang Gao, Yubing Huang, Wanqing Wu, Kefan Huang and Huanfeng Jiang
Chemical Communications 2014 - vol. 50(Issue 61) pp:NaN8373-8373
Publication Date(Web):2014/06/18
DOI:10.1039/C4CC03062A
An efficient Pd-catalyzed oxidative cyclization reaction for the synthesis of functionalized indolines by direct C–H activation of acetanilide has been developed. The norbornylpalladium species formed via direct ortho C–H activation of acetanilides is supposed to be a key intermediate in this transformation.
Co-reporter:Yang Gao, Wanqing Wu, Huawen Huang, Yubing Huang and Huanfeng Jiang
Chemical Communications 2014 - vol. 50(Issue 7) pp:NaN848-848
Publication Date(Web):2013/10/31
DOI:10.1039/C3CC47310D
A novel and efficient Pd-catalyzed intermolecular [3 + 2] carbocyclization of alkynols and electron-deficient alkynes for the synthesis of halo-cyclopentadienes (Cps) has been developed. The present protocol employs simple propargyl alcohols as the C3 group to participate in the cyclization reaction, providing a highly convenient and atom-economical entry to the halo-cyclopentadiene framework.
Co-reporter:Jianxiao Li, Weigao Hu, Chunsheng Li, Shaorong Yang, Wanqing Wu and Huanfeng Jiang
Inorganic Chemistry Frontiers 2017 - vol. 4(Issue 3) pp:NaN376-376
Publication Date(Web):2016/12/12
DOI:10.1039/C6QO00633G
A novel and efficient palladium-catalyzed aerobic cascade reaction of haloalkynes with unactivated alkenes for synthesis of functionalized oxetanes has been demonstrated. This cascade protocol, including chloropalladation and a Heck-like process, proceeds smoothly with good functional group tolerance and high selectivity.
Co-reporter:Pengquan Chen, Chuanle Zhu, Rui Zhu, Zhiming Lin, Wanqing Wu and Huanfeng Jiang
Organic & Biomolecular Chemistry 2017 - vol. 15(Issue 5) pp:NaN1235-1235
Publication Date(Web):2017/01/05
DOI:10.1039/C6OB02137A
A palladium-catalyzed cyclopropanation of internal alkenes with N-tosylhydrazones is presented. This gram-scale cyclopropanation reaction of maleimides provides a wide spectrum of 3-azabicyclo[3.1.0]hexane derivatives in high yields and diastereoselectivities. The major diastereoisomers could be easily isolated by chromatography on silica gel. This protocol provides a practical route to the mu opioid receptor antagonist CP-866,087.
Co-reporter:Yue Yu, Yang Chen, Wanqing Wu and Huanfeng Jiang
Chemical Communications 2017 - vol. 53(Issue 3) pp:NaN643-643
Publication Date(Web):2016/12/09
DOI:10.1039/C6CC08320J
We have developed a Michael-addition/cyclization procedure between ene–yne–ketones and TMSCN under metal-free conditions. A wide range of cyanofurans was delivered in high yields, which could be further transformed to a series of furo-furanimines, furo-pyridazines or carboxamido-furans. In addition, deuterium-labeling experiments have been conducted to clarify the reaction pathway.
Co-reporter:Huanfeng Jiang, Wei Huang, Yue Yu, Songjian Yi, Jiawei Li and Wanqing Wu
Chemical Communications 2017 - vol. 53(Issue 54) pp:NaN7476-7476
Publication Date(Web):2017/06/12
DOI:10.1039/C7CC03125D
We have developed a transition-metal free trifluoromethylation protocol between enamines and CF3SO2Na. A wide range of β-trifluoromethyl substituted enamines were delivered in moderate to high yields with only E-configurations.
Co-reporter:Wei Guo, Dongqing Liu, Jianhua Liao, Fanghua Ji, Wanqing Wu and Huanfeng Jiang
Inorganic Chemistry Frontiers 2017 - vol. 4(Issue 6) pp:
Publication Date(Web):
DOI:10.1039/C6QO00842A
Co-reporter:Jianxiao Li, Yanni An, Jiawei Li, Shaorong Yang, Wanqing Wu and Huanfeng Jiang
Inorganic Chemistry Frontiers 2017 - vol. 4(Issue 8) pp:
Publication Date(Web):
DOI:10.1039/C7QO00215G
Co-reporter:Chuanle Zhu, Pengquan Chen, Rui Zhu, Zhiming Lin, Wanqing Wu and Huanfeng Jiang
Chemical Communications 2017 - vol. 53(Issue 18) pp:NaN2700-2700
Publication Date(Web):2017/02/03
DOI:10.1039/C6CC10187A
A new example of CN double bond formation in metal carbene insertion reactions is reported. Remarkably, the general 1,2-migration process of the corresponding ylide intermediates in X–H carbene insertion reactions that leads to C–X single bond formation is completely inhibited by replacing the H atom with a nitrogen atom. This palladium-catalyzed carbene insertion reaction with NN double bonds gave various N,N-disubstituted hydrazone products in high yields.
Co-reporter:Zun Li, Jia Zheng, Weigao Hu, Jianxiao Li, Wanqing Wu and Huanfeng Jiang
Inorganic Chemistry Frontiers 2017 - vol. 4(Issue 7) pp:
Publication Date(Web):
DOI:10.1039/C7QO00082K