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Yingsheng Zhao

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Name: 赵应声; Zhao, YingSheng
Organization: Soochow University , China
Department: College of Chemistry
Title: Associate Professor(PhD)

TOPICS

Ligand-Enabled Regioselectivity in the Oxidative Cross-coupling of Arenes with Toluenes and Cycloalkanes Using Ruthenium Catalysts: Tuning the Site-Selectivity from the ortho to meta Positions
Co-reporter:Guobao Li, Dongze Li, Jingyu Zhang, Da-Qing Shi, and Yingsheng Zhao
ACS Catalysis June 2, 2017 Volume 7(Issue 6) pp:4138-4138
Publication Date(Web):May 10, 2017
DOI:10.1021/acscatal.7b01072
A Ru-catalyzed 1,1′-binaphthyl-2,2′-diylhydrogen phosphate (BNDHP)-enabled meta C–H benzylation under the assistance of ferrocene using less sterically hindered toluene derivatives as the coupling partners has been developed. Various arenes bearing pyridyl, pyridmidyl, and pyrazolyl directing groups can be selectively coupled with toluenes at the meta positions in moderate to good yield. A mechanistic study clearly showed the site selectivity at the ortho or meta position is completely controlled by the ligand of BNDHP and the catalyst precursor.Keywords: C−H benzylation; Oxidative Cross-coupling; Regioselectivity; Ruthenium Catalyst;
Ligand-Enabled Regioselectivity in the Oxidative Cross-coupling of Arenes with Toluenes and Cycloalkanes Using Ruthenium Catalysts: Tuning the Site-Selectivity from the ortho to meta Positions
Co-reporter:Guobao Li, Dongze Li, Jingyu Zhang, Da-Qing Shi, and Yingsheng Zhao
ACS Catalysis June 2, 2017 Volume 7(Issue 6) pp:4138-4138
Publication Date(Web):May 10, 2017
DOI:10.1021/acscatal.7b01072
A Ru-catalyzed 1,1′-binaphthyl-2,2′-diylhydrogen phosphate (BNDHP)-enabled meta C–H benzylation under the assistance of ferrocene using less sterically hindered toluene derivatives as the coupling partners has been developed. Various arenes bearing pyridyl, pyridmidyl, and pyrazolyl directing groups can be selectively coupled with toluenes at the meta positions in moderate to good yield. A mechanistic study clearly showed the site selectivity at the ortho or meta position is completely controlled by the ligand of BNDHP and the catalyst precursor.Keywords: C−H benzylation; Oxidative Cross-coupling; Regioselectivity; Ruthenium Catalyst;
Ruthenium-Catalyzed Carbonylation of Oxalyl Amide-Protected Benzylamines with Isocyanate as the Carbonyl Source
Co-reporter:Jian Han, Ning Wang, Zhi-Bin Huang, Yingsheng Zhao, and Da-Qing Shi
The Journal of Organic Chemistry July 7, 2017 Volume 82(Issue 13) pp:6831-6831
Publication Date(Web):June 15, 2017
DOI:10.1021/acs.joc.7b00975
An efficient synthesis of isoindolin-1-ones from oxalyl amide-protected benzylamines, through ruthenium-catalyzed intramolecular C(sp2)-H carbonylation, has been developed. Variously substituted benzylamines could be well tolerated in this new protocol, affording the corresponding products in moderate to excellent yields. This approach constitutes the first example of Ru(II)-catalyzed C(sp2)-H carbonylation with isocyanate as a novel commercially available carbonyl source.
Rhodium(III)-Catalyzed Selective Monoarylation of β or γ C(sp3)–H Bonds Assisted by a Trimethylpyrazole Group
Co-reporter:Guangliang Tu;Chunchen Yuan
Organic Letters January 20, 2017 Volume 19(Issue 2) pp:356-359
Publication Date(Web):December 30, 2016
DOI:10.1021/acs.orglett.6b03522
The selective arylation of unactivated β or challenging γ primary and secondary β-C(sp3)–H bonds has been developed with a Cp*Rh(III) catalyst assisted by a trimethylpyrazole group. A rarely reported six-membered rhodacycle has been identified in rhodium-catalyzed C(sp3)–H activation reactions. Preliminary mechanistic studies have revealed that a concerted metalation–deprotonation pathway might be involved in the C–H activation step.
Ruthenium-Catalyzed Difluoroalkylation of 8-Aminoquinoline Amides at the C5-Position
Co-reporter:Changpeng Chen;Runsheng Zeng;Jingyu Zhang
European Journal of Organic Chemistry 2017 Volume 2017(Issue 46) pp:6947-6950
Publication Date(Web):2017/12/15
DOI:10.1002/ejoc.201701150
A ruthenium-catalyzed highly selective difluoromethylation of 8-aminoquinoline amides at the C5 position has been developed. It tolerates a broad range of functional groups, providing the corresponding difluoromethylated products in moderate to good yields. Preliminary experimental results indicate that the tricoordinate ruthenium intermediate is the key factor in achieving the C5-position selectivity.
Palladium/silver reagent-promoted aryl phosphorylation: flexible synthesis of substituted-3-benzylidene-2-(2-(diphenylphosphoryl)-aryl)-isoindolin-1-one
Co-reporter:Peng Shi;Qing Wang;Xiao Zeng;Runsheng Zeng
RSC Advances (2011-Present) 2017 vol. 7(Issue 85) pp:54277-54280
Publication Date(Web):2017/11/21
DOI:10.1039/C7RA10902D
A novel Pd(OAc)2/Ag2CO3-catalyzed coupling reaction was investigated. Substituted 3-benzylidene-2-arylisoindolin-1-ones were reacted with diphenylphosphine oxide to afford 3-arylidene-2-(2-(diphenylphosphoryl)aryl)isoindolin-1-ones. The reaction proceeded at 25 °C in an air atmosphere in the absence of base and ligands. Our results indicate that the diphenylphosphine oxide free radical tends to attack the aryl rather than the double bond in this reaction.
A practical approach for the synthesis of oxindole and isatin derivatives by Pd-catalyzed intramolecular amination
Co-reporter:Yubo Pang;Mingyu Guan;Runsheng Zeng
Organic Chemistry Frontiers 2017 vol. 4(Issue 12) pp:2408-2411
Publication Date(Web):2017/11/21
DOI:10.1039/C7QO00710H
Oxindole/isatin-N-acetamide derivatives are a class of important pharmacologically active compounds. Herein, we report a practical protocol for the synthesis of such derivatives based on palladium-catalyzed intramolecular amination. Various functional groups are tolerated, and the corresponding products are obtained in moderate to good yields, highlighting the potential synthetic utility of this method.
Pd-Catalyzed regioselective sequential meta-, ortho-C–H functionalization of arenes: a predictable approach to the synthesis of polysubstituted β-arylethylamines
Co-reporter:Jian Han;Ning Wang;Zhi-Bin Huang;Da-Qing Shi
Organic & Biomolecular Chemistry 2017 vol. 15(Issue 24) pp:5112-5116
Publication Date(Web):2017/06/21
DOI:10.1039/C7OB01135K
With the assistance of the same bidentate directing group, the first example of sequential, controllable C–H functionalization of β-arylethylamines at different positions for the construction of polysubstituted arenes is reported. Pd-Catalyzed highly regioselective ortho-C–H functionalization reactions of meta-aryl substituted arylethylamines are performed, including alkynylation, iodination, acetoxylation and amination, which led to a concise approach to the synthesis of polysubstituted β-arylethylamine derivatives.
Pd-Catalyzed thiophene directed regioselective functionalization of arenes: a direct approach to multiply-substituted benzyl amines
Co-reporter:Jundie Hu;Guobao Li;Zhi-Bin Huang;Jingyu Zhang;Da-Qing Shi
Organic Chemistry Frontiers 2017 vol. 4(Issue 8) pp:1503-1507
Publication Date(Web):2017/07/26
DOI:10.1039/C7QO00236J
The first example of employing thiophene as the coordination center to assist C–H functionalization via a palladium catalyst has been described. The synthetically challenging penta-substituted benzylamines with five different functional groups could be easily achieved by taking advantage of transitive oxalyl amide/thiophene-directed C–H functionalization, which highlights its versatility in the construction of multiply-substituted arenes. The penta-substituted benzylamine displays its potential nature as a hole-transporting material.
Palladium-catalyzed direct ortho-alkynylation of arylalkylacid derivatives at γ and δ positions via an N,O-bidentate directing group
Co-reporter:Guobao Li;Pei Liu;Jingyu Zhang;Da-Qing Shi
Organic Chemistry Frontiers 2017 vol. 4(Issue 10) pp:1931-1934
Publication Date(Web):2017/09/26
DOI:10.1039/C7QO00327G
Palladium-catalyzed ortho-alkynylation of arylalkylacid derivatives at remote γ and δ positions with the assistance of an N,O-bidentate directing group of glycine dimethylamide (GDMA) is reported for the first time. A wide variety of phenylacetic acid and 3-phenylpropionic acid derivatives is tolerated in this protocol, which provides a general means to synthesize substituted alkynylarylalkyl acid derivatives.
meta-Selective C–H difluoromethylation of various arenes with a versatile ruthenium catalyst
Co-reporter:C. C. Yuan;X. L. Chen;J. Y. Zhang;Y. S. Zhao
Organic Chemistry Frontiers 2017 vol. 4(Issue 9) pp:1867-1871
Publication Date(Web):2017/08/22
DOI:10.1039/C7QO00449D
A ruthenium-enabled meta-selective C–H difluoromethylation of arenes has been developed. Various arenes bearing pyridyl, pyrazolyl, imidazolyl, or pyrimidyl directing groups, or removable oxazoline directing groups, were tolerated in this meta-selective C–H difluoromethylation, affording the difluoromethylated products in moderate to good yields. The difluoromethyl group could be selectively installed into several drug molecules and bioactive compounds in one step, highlighting the synthetic utility and importance of this new method.
Rhodium(III)-Catalyzed Oxidative C–H/C–H Cross-Coupling of Heteroarenes and Masked Benzylamines
Co-reporter:Jundie Hu, Guobao Li, Chunchen Yuan, Zhi-Bin Huang, Da-Qing Shi, and Yingsheng Zhao
Organic Letters 2016 Volume 18(Issue 23) pp:5998-6001
Publication Date(Web):November 15, 2016
DOI:10.1021/acs.orglett.6b02773
The first example of oxidative C–H/C–H cross-coupling of oxalyl amide-protected benzylamines and various heteroarenes in the presence of a rhodium(III) catalyst has been developed. The route provides a means of synthesizing ortho-heteroarylated benzylamines. The methodology presents broad substrate scope, great functional group tolerance, and good to excellent yields in the synthesis of substituted benzylamines. The study also reveals that the thienoisoquinoline derivatives can be accessed through the intramolecular amination of thiophenyl-substituted benzylamines with palladium(II).
Highly regioselective meta arylation of oxalyl amide-protected β-arylethylamine via the Catellani reaction
Co-reporter:Jian Han, Li Zhang, Yan Zhu, Yongxiang Zheng, Xiaolan Chen, Zhi-Bin Huang, Da-Qing Shi and Yingsheng Zhao  
Chemical Communications 2016 vol. 52(Issue 42) pp:6903-6906
Publication Date(Web):27 Apr 2016
DOI:10.1039/C6CC02384C
The first bidentate directing group assisted highly selective meta arylation of β-arylethylamine derivatives via palladium/norbornene catalysis is reported, and the range of aryl iodides for the oxalyl amide assisted meta-selective arylation reactions is broadest yet reported. This meta arylation also proceeds well with thiophene derivatives, giving the corresponding products in satisfactory yields. And three-step functionalization of arylethyloxalamide with three different functional groups is successfully performed.
Pd-Catalyzed sequential β-C(sp3)–H arylation and intramolecular amination of δ-C(sp2)–H bonds for synthesis of quinolinones via an N,O-bidentate directing group
Co-reporter:Mingyu Guan, Yubo Pang, Jingyu Zhang and Yingsheng Zhao  
Chemical Communications 2016 vol. 52(Issue 43) pp:7043-7046
Publication Date(Web):27 Apr 2016
DOI:10.1039/C6CC02865A
The pharmacological importance of 2-quinolinone derivatives is well known. Herein, we developed an effective protocol for the synthesis of 2-quinolinone derivatives by palladium-catalyzed sequential β-C(sp3)–H arylation and selective intramolecular C(sp2)–H/N–H amination starting with aryl iodides and carboxylic acids. A novel directing group, glycine dimethylamide, was used in the synthesis. We synthesized various quinolinone derivatives, including 5-substituted quinolinones, which are difficult to obtain using the traditional pathway. The directing group could be easily removed and could be readily transformed into other useful functional groups.
Transformation of masked benzyl alcohols to o-aminobenzaldehydes through C–H activation: a facile approach to quinazolines
Co-reporter:Xiaolan Chen, Jian Han, Yan Zhu, Chunchen Yuan, Jingyu Zhang and Yingsheng Zhao  
Chemical Communications 2016 vol. 52(Issue 67) pp:10241-10244
Publication Date(Web):21 Jul 2016
DOI:10.1039/C6CC05560E
Direct transformation of a directing group to important synthetic units would provide a high atom efficiency synthetic approach in synthetic chemistry. Herein, a convenient protocol for the synthesis of o-aminobenzaldehyde and benzoxazole derivatives from benzyl alcohols has been developed by employing (N,N-dimethyl)oxamoyl amide as a directing group in a palladium-catalyzed intramolecular amination. Furthermore, the attached directing center may not only be transformed into the product, but may also be further applied to generate synthetically important quinazoline and quinoline units. Finally, a high atom efficiency one-pot, two-step approach to form quinazolines from benzyl alcohol derivatives has been achieved in good yields, thus demonstrating its high utility.
Pd-Catalyzed Coupling of γ-C(sp3)–H Bonds of Oxalyl Amide-Protected Amino Acids with Heteroaryl and Aryl Iodides
Co-reporter:Jian Han, Yongxiang Zheng, Chao Wang, Yan Zhu, Zhi-Bin Huang, Da-Qing Shi, Runsheng Zeng, and Yingsheng Zhao
The Journal of Organic Chemistry 2016 Volume 81(Issue 13) pp:5681-5689
Publication Date(Web):June 10, 2016
DOI:10.1021/acs.joc.6b00649
Pd-catalyzed regioselective coupling of γ-C(sp3)–H bonds of oxalyl amide-protected amino acids with heteroaryl and aryl iodides is reported. A wide variety of iodides are tolerated, giving the corresponding products in moderate to good yields. Various oxalyl amide-protected amino acids were compatible in this C–H transformation, thus representing a practical method for constructing non-natural amino acid derivatives.
Palladium-Catalyzed Carbonylation of β-Arylethylamide Directed by Oxalyl Amide in the Presence of Carbon Monoxide
Co-reporter:Li Zhang, Chao Wang, Jian Han, Zhi-Bin Huang, and Yingsheng Zhao
The Journal of Organic Chemistry 2016 Volume 81(Issue 12) pp:5256-5262
Publication Date(Web):May 23, 2016
DOI:10.1021/acs.joc.6b00932
Pd-catalyzed regioselective coupling of β-C(sp2)–H bonds in aromatic amines protected by oxalyl amide with carbon monoxide is reported. The reaction could tolerate various functional groups and could afford good to excellent yields of the corresponding 3,4-dihydroisoquinolinone derivatives. Remarkably, it could also tolerate β-arylethylamino acid and thiopheneethylamine derivatives, thus showing their potential for producing several important units for bioactive compound synthesis.
Oxalyl amide assisted palladium-catalyzed synthesis of pyrrolidones via carbonylation of γ-C(sp3)–H bonds of aliphatic amine substrates
Co-reporter:Chao Wang, Li Zhang, Changpeng Chen, Jian Han, Yingming Yao and Yingsheng Zhao  
Chemical Science 2015 vol. 6(Issue 8) pp:4610-4614
Publication Date(Web):19 May 2015
DOI:10.1039/C5SC00519A
The first Pd-catalyzed regioselective γ-carbonylation of oxalyl amide protected aliphatic amines with carbon monoxide leading to synthesis of pyrrolidones has been developed. Both γ-methyl and cyclopropyl methylene C–H bonds are well activated to obtain the corresponding pyrrolidones in moderate to excellent yields. The role of 3-(trifluoromethyl)benzoic acid as an additive is critical as it helps in stabilizing the palladium intermediate formed during the catalytic cycle. The reaction scope is extended to benzylamine and allyl amine derivatives, thereby affording the corresponding products in good to excellent yields.
Palladium-catalyzed oxalyl amide assisted direct ortho-alkynylation of arylalkylamine derivatives at δ and ε positions
Co-reporter:Mingyu Guan, Changpeng Chen, Jingyu Zhang, Runsheng Zeng and Yingsheng Zhao  
Chemical Communications 2015 vol. 51(Issue 60) pp:12103-12106
Publication Date(Web):19 Jun 2015
DOI:10.1039/C5CC04390E
Palladium-catalyzed oxalyl amide directed ortho-alkynylation of arylalkylamine derivatives is reported for the first time. A wide variety of β-arylethamine and γ-arylpropamine derivatives are compatible with this protocol. This method provides a general means to synthesize substituted alkynylarylalkylamine derivatives, highlighting the ability of oxalyl amide in promoting C–H functionalization at unique δ and ε positions.
Palladium-Catalyzed Oxalyl Amide Directed Silylation and Germanylation of Amine Derivatives
Co-reporter:Changpeng Chen, Mingyu Guan, Jingyu Zhang, Zhenkang Wen, and Yingsheng Zhao
Organic Letters 2015 Volume 17(Issue 15) pp:3646-3649
Publication Date(Web):July 10, 2015
DOI:10.1021/acs.orglett.5b01393
Palladium-catalyzed direct ortho-silylation of oxalyl amide-protected phenylmethanamine and phenethylamine with commercially available disilanes is reported. Germanylation products were also produced under the same reaction conditions. This protocol tolerated oxalyl amide-protected aliphatic amines, which gave γ-C–H silylation products.
Direct ortho-C–H Functionalization of Aromatic Alcohols Masked by Acetone Oxime Ether via exo-Palladacycle
Co-reporter:Kun Guo, Xiaolan Chen, Mingyu Guan, and Yingsheng Zhao
Organic Letters 2015 Volume 17(Issue 7) pp:1802-1805
Publication Date(Web):March 13, 2015
DOI:10.1021/acs.orglett.5b00594
A simple and practical exo-oxime ether auxilixary for ortho-C–H functionalization of aromatic alcohols has been developed. Selective olefination of aromatic alcohols were first achieved via a six- or seven-membered exo-acetone oxime ether palladacycle with broad substrate scope. In addition, the crystal of the exo-palladacycle intermediate was obtained for the first time, and the application of this method in total synthesis of 3-deoxyisoochracinic acid was accomplished via a novel retro-synthetic disconnection approach, thus demonstrating the utility of this transformation.
Palladium(II)-catalyzed Sequential ortho-olefination of β-arylethamines with assistance of oxalyl amide
Co-reporter:Pei Liu, Jian Han, Qian Wang, Zhibin Huang, Daqing Shi, Runsheng Zeng and Ying Sheng Zhao  
RSC Advances 2015 vol. 5(Issue 74) pp:60646-60649
Publication Date(Web):06 Jul 2015
DOI:10.1039/C5RA11677E
Pd-catalyzed highly selective ortho-alkenylation of β-arylethamines with the assistance of oxalyl amide is developed. A wide range of olefins such as allyl acetate, allyl alcohol derivatives, terminal alkenes, acraldehyde, acrylate, acrylonitrile, neohexene and styrene derivatives are all tolerable, which is the broadest yet reported for this kind of C–H transformation. Furthermore, sequential functionalization of β-arylethamine is also achieved well in one pot.
Palladium-catalyzed oxygenation of C(sp2)–H and C(sp3)–H bonds under the assistance of oxalyl amide
Co-reporter:Pei Liu, Jian Han, Chang Peng Chen, Da Qing Shi and Ying Sheng Zhao  
RSC Advances 2015 vol. 5(Issue 36) pp:28430-28434
Publication Date(Web):17 Mar 2015
DOI:10.1039/C5RA00114E
A practical palladium-catalyzed γ-oxygenation of C(sp2)–H and C(sp3)–H bonds under the assistance of oxalyl amide with PhI(OAc)2 as oxidant was developed. Selective alkoxylation or acetoxylation of oxalyl amide protected benzyl amine was achieved in high yield. The oxalyl amide protected α-substituted propylamines could be transformed into acetoxylated products in good to excellent yields.
Palladium(II)-Catalyzed Acetoxime Directed ortho-Arylation of Aromatic Alcohols
Co-reporter:Kun Guo;Xiaolan Chen;Dr. Jingyu Zhang;Dr. Yingsheng Zhao
Chemistry - A European Journal 2015 Volume 21( Issue 48) pp:17474-17478
Publication Date(Web):
DOI:10.1002/chem.201503284

Abstract

Biaryls, which contained a benzyloxy motif, were directly constructed through a ligand-promoted PdII-catalyzed ortho-arylation of masked aromatic alcohols. A variety of acetoxime ethers could be coupled with a diverse range of arylboronic acid pinocol esters, giving direct access to bioactive biaryls in modest to good yield. Not only could acetoxime be subsequently removed without a separation, functionalized hydroxylamine derivatives could also be obtained.

Palladium-Catalyzed Oxalyl Amide-Directed γ-Arylation of Aliphatic Amines
Co-reporter:Jian Han, Yongxiang Zheng, Chao Wang, Yan Zhu, Da-Qing Shi, Runsheng Zeng, Zhi-Bin Huang, and Yingsheng Zhao
The Journal of Organic Chemistry 2015 Volume 80(Issue 18) pp:9297-9306
Publication Date(Web):August 26, 2015
DOI:10.1021/acs.joc.5b00968
A method for palladium-catalyzed oxalyl amide-directed arylation of α-unsubstituted aliphatic amines with aryl iodides has been developed. A wide variety of aryl iodides are tolerated in this transformation, affording various γ-arylpropylamine derivatives. Heterocyclic iodides can also be competent reagents in this γ-C(sp3)–H bonds transformation.
Palladium-Catalyzed ortho-Olefination of Phenyl Acetic and Phenyl Propylacetic Esters via C–H Bond Activation
Co-reporter:Jundie Hu, Mingyu Guan, Jian Han, Zhi-Bin Huang, Da-Qing Shi, and Yingsheng Zhao
The Journal of Organic Chemistry 2015 Volume 80(Issue 16) pp:7896-7904
Publication Date(Web):July 21, 2015
DOI:10.1021/acs.joc.5b00775
A highly regioselective palladium-catalyzed ester-directed ortho-olefination of phenyl acetic and propionic esters with olefins via C–H bond activation has been developed. A wide variety of phenyl acetic and propionic esters were tolerated in this transformation, affording the corresponding olefinated aromatic compounds. The ortho-olefination of heterocyclic acetic and propionic esters also took place smoothly giving the products in good yields, thus proving the potential utility of this protocol in synthetic chemistry.
Palladium-Catalyzed ortho-Selective C–H Fluorination of Oxalyl Amide-Protected Benzylamines
Co-reporter:Changpeng Chen, Chao Wang, Jingyu Zhang, and Yingsheng Zhao
The Journal of Organic Chemistry 2015 Volume 80(Issue 2) pp:942-949
Publication Date(Web):December 9, 2014
DOI:10.1021/jo502365b
A novel and efficient synthetic method for o-fluorobenzylamines via palladium catalyst using an easily accessible oxalyl amide as directing group has been developed. The cheap N-fluorobenzenesulfonimide could be used as an effective [F+] source and t-amyl-OH as the solvent with Pd(OAc)2 as catalyst. Selective mono- or difluorination of oxalyl amide-protected benzylamine derivatives were achieved by modifying the reaction conditions, which presented an efficient method for the preparation of ortho-fluorinated benzylamines.
Highly site-selective sequential alkenylation of oxalyl amide protected phenylpropylamine derivatives via a seven-membered palladacycle
Co-reporter:Qian Wang, Jian Han, Chao Wang, Jingyu Zhang, Zhibin Huang, Daqing Shi and Yingsheng Zhao  
Chemical Science 2014 vol. 5(Issue 12) pp:4962-4967
Publication Date(Web):20 Aug 2014
DOI:10.1039/C4SC02172J
A protocol for palladium-catalyzed ortho C(sp2)–H alkenylation via a rarely reported seven-membered palladacycle with oxalyl amide as a directing group was reported. The range of olefins was the broadest yet reported for this kind of C–H alkenylation reaction. For example, allyl acetate, allyl alcohol derivatives, acraldehyde, acrylate and acrylonitrile were all tolerated in this C–H transformation. Sequential alkenylation reactions were also achieved to construct the complex olefinated arenes in good yields in one pot.
Oxalyl Amide Assisted Palladium-Catalyzed Arylation of C(sp2)–H Bond at the δ Position
Co-reporter:Jian Han, Pei Liu, Chao Wang, Qian Wang, Jingyu Zhang, Yanwei Zhao, Daqing Shi, Zhibin Huang, and Yingsheng Zhao
Organic Letters 2014 Volume 16(Issue 21) pp:5682-5685
Publication Date(Web):October 16, 2014
DOI:10.1021/ol502745g
A successful protocol has been developed for δ-arylation of β-arylethamines at the ortho position under mild conditions. The newly developed methodology first presents broad substrate scope, great functional group tolerance, and good to excellent yield in the synthesis of substituted β-arylethylamines. The transformation represents a practical advantage of oxalyl amide in assistance with C–H functionalization at a remote position.
Practical organic solvent-free Cu(OAc)2/DMAP/TEMPO-catalyzed aldehyde and imine formation from alcohols under air atmosphere
Co-reporter:Mingyu Guan, Chao Wang, Jingyu Zhang and Yingsheng Zhao  
RSC Advances 2014 vol. 4(Issue 90) pp:48777-48782
Publication Date(Web):17 Sep 2014
DOI:10.1039/C4RA09851J
A highly efficient and practical organic solvent-free Cu(OAc)2/DMAP/TEMPO catalyst system for the selective aerobic oxidation of benzylic and allylic alcohols to aldehydes and phenones under an ambient air atmosphere was reported. A wide range of functional groups such as phenolic hydroxyl, amino, and methylthio are compatible with the catalyst system. The organic solvent-free aerobic oxidative imine synthesis from benzyl alcohol and amines was also achieved via the newly developed Cu(OAc)2/DMAP/TEMPO catalyst. 100 g-scale reactions for aldehyde and imine formation were achieved with over 90% yield using 0.5 mol% catalyst loading in 36 hours, presenting a potential valuable protocol for both economical and environmental considerations.
Easily Accessible Auxiliary for Palladium-Catalyzed Intramolecular Amination of C(sp2)H and C(sp3)H Bonds at - and -Positions
Co-reporter:Chao Wang;Changpeng Chen;Jingyu Zhang;Jian Han;Qian Wang;Kun Guo;Pei Liu;Mingyu Guan;Dr. Yingming Yao;Dr. Yingsheng Zhao
Angewandte Chemie International Edition 2014 Volume 53( Issue 37) pp:9884-9888
Publication Date(Web):
DOI:10.1002/anie.201404854

Abstract

An easily synthesized and accessible N,O-bidentate auxiliary has been developed for selective CH activation under palladium catalysis. The novel auxiliary showed its first powerful application in CH functionalization of remote positions. Both C(sp2)H and C(sp3)H bonds at δ- and ε-positions were effectively activated, thus giving tetrahydroquinolines, benzomorpholines, pyrrolidines, and indolines in moderate to excellent yields by palladium-catalyzed intramolecular CH amination.

Pd-Catalyzed regioselective sequential meta-, ortho-C–H functionalization of arenes: a predictable approach to the synthesis of polysubstituted β-arylethylamines
Co-reporter:Jian Han, Ning Wang, Zhi-Bin Huang, Yingsheng Zhao and Da-Qing Shi
Organic & Biomolecular Chemistry 2017 - vol. 15(Issue 24) pp:NaN5116-5116
Publication Date(Web):2017/05/30
DOI:10.1039/C7OB01135K
With the assistance of the same bidentate directing group, the first example of sequential, controllable C–H functionalization of β-arylethylamines at different positions for the construction of polysubstituted arenes is reported. Pd-Catalyzed highly regioselective ortho-C–H functionalization reactions of meta-aryl substituted arylethylamines are performed, including alkynylation, iodination, acetoxylation and amination, which led to a concise approach to the synthesis of polysubstituted β-arylethylamine derivatives.
Pd-Catalyzed thiophene directed regioselective functionalization of arenes: a direct approach to multiply-substituted benzyl amines
Co-reporter:Jundie Hu, Guobao Li, Zhi-Bin Huang, Jingyu Zhang, Da-Qing Shi and Yingsheng Zhao
Inorganic Chemistry Frontiers 2017 - vol. 4(Issue 8) pp:
Publication Date(Web):
DOI:10.1039/C7QO00236J
Highly regioselective meta arylation of oxalyl amide-protected β-arylethylamine via the Catellani reaction
Co-reporter:Jian Han, Li Zhang, Yan Zhu, Yongxiang Zheng, Xiaolan Chen, Zhi-Bin Huang, Da-Qing Shi and Yingsheng Zhao
Chemical Communications 2016 - vol. 52(Issue 42) pp:NaN6906-6906
Publication Date(Web):2016/04/27
DOI:10.1039/C6CC02384C
The first bidentate directing group assisted highly selective meta arylation of β-arylethylamine derivatives via palladium/norbornene catalysis is reported, and the range of aryl iodides for the oxalyl amide assisted meta-selective arylation reactions is broadest yet reported. This meta arylation also proceeds well with thiophene derivatives, giving the corresponding products in satisfactory yields. And three-step functionalization of arylethyloxalamide with three different functional groups is successfully performed.
Pd-Catalyzed sequential β-C(sp3)–H arylation and intramolecular amination of δ-C(sp2)–H bonds for synthesis of quinolinones via an N,O-bidentate directing group
Co-reporter:Mingyu Guan, Yubo Pang, Jingyu Zhang and Yingsheng Zhao
Chemical Communications 2016 - vol. 52(Issue 43) pp:NaN7046-7046
Publication Date(Web):2016/04/27
DOI:10.1039/C6CC02865A
The pharmacological importance of 2-quinolinone derivatives is well known. Herein, we developed an effective protocol for the synthesis of 2-quinolinone derivatives by palladium-catalyzed sequential β-C(sp3)–H arylation and selective intramolecular C(sp2)–H/N–H amination starting with aryl iodides and carboxylic acids. A novel directing group, glycine dimethylamide, was used in the synthesis. We synthesized various quinolinone derivatives, including 5-substituted quinolinones, which are difficult to obtain using the traditional pathway. The directing group could be easily removed and could be readily transformed into other useful functional groups.
Transformation of masked benzyl alcohols to o-aminobenzaldehydes through C–H activation: a facile approach to quinazolines
Co-reporter:Xiaolan Chen, Jian Han, Yan Zhu, Chunchen Yuan, Jingyu Zhang and Yingsheng Zhao
Chemical Communications 2016 - vol. 52(Issue 67) pp:NaN10244-10244
Publication Date(Web):2016/07/21
DOI:10.1039/C6CC05560E
Direct transformation of a directing group to important synthetic units would provide a high atom efficiency synthetic approach in synthetic chemistry. Herein, a convenient protocol for the synthesis of o-aminobenzaldehyde and benzoxazole derivatives from benzyl alcohols has been developed by employing (N,N-dimethyl)oxamoyl amide as a directing group in a palladium-catalyzed intramolecular amination. Furthermore, the attached directing center may not only be transformed into the product, but may also be further applied to generate synthetically important quinazoline and quinoline units. Finally, a high atom efficiency one-pot, two-step approach to form quinazolines from benzyl alcohol derivatives has been achieved in good yields, thus demonstrating its high utility.
Palladium-catalyzed oxalyl amide assisted direct ortho-alkynylation of arylalkylamine derivatives at δ and ε positions
Co-reporter:Mingyu Guan, Changpeng Chen, Jingyu Zhang, Runsheng Zeng and Yingsheng Zhao
Chemical Communications 2015 - vol. 51(Issue 60) pp:NaN12106-12106
Publication Date(Web):2015/06/19
DOI:10.1039/C5CC04390E
Palladium-catalyzed oxalyl amide directed ortho-alkynylation of arylalkylamine derivatives is reported for the first time. A wide variety of β-arylethamine and γ-arylpropamine derivatives are compatible with this protocol. This method provides a general means to synthesize substituted alkynylarylalkylamine derivatives, highlighting the ability of oxalyl amide in promoting C–H functionalization at unique δ and ε positions.
Oxalyl amide assisted palladium-catalyzed synthesis of pyrrolidones via carbonylation of γ-C(sp3)–H bonds of aliphatic amine substrates
Co-reporter:Chao Wang, Li Zhang, Changpeng Chen, Jian Han, Yingming Yao and Yingsheng Zhao
Chemical Science (2010-Present) 2015 - vol. 6(Issue 8) pp:NaN4614-4614
Publication Date(Web):2015/05/19
DOI:10.1039/C5SC00519A
The first Pd-catalyzed regioselective γ-carbonylation of oxalyl amide protected aliphatic amines with carbon monoxide leading to synthesis of pyrrolidones has been developed. Both γ-methyl and cyclopropyl methylene C–H bonds are well activated to obtain the corresponding pyrrolidones in moderate to excellent yields. The role of 3-(trifluoromethyl)benzoic acid as an additive is critical as it helps in stabilizing the palladium intermediate formed during the catalytic cycle. The reaction scope is extended to benzylamine and allyl amine derivatives, thereby affording the corresponding products in good to excellent yields.
Highly site-selective sequential alkenylation of oxalyl amide protected phenylpropylamine derivatives via a seven-membered palladacycle
Co-reporter:Qian Wang, Jian Han, Chao Wang, Jingyu Zhang, Zhibin Huang, Daqing Shi and Yingsheng Zhao
Chemical Science (2010-Present) 2014 - vol. 5(Issue 12) pp:NaN4967-4967
Publication Date(Web):2014/08/20
DOI:10.1039/C4SC02172J
A protocol for palladium-catalyzed ortho C(sp2)–H alkenylation via a rarely reported seven-membered palladacycle with oxalyl amide as a directing group was reported. The range of olefins was the broadest yet reported for this kind of C–H alkenylation reaction. For example, allyl acetate, allyl alcohol derivatives, acraldehyde, acrylate and acrylonitrile were all tolerated in this C–H transformation. Sequential alkenylation reactions were also achieved to construct the complex olefinated arenes in good yields in one pot.
4-chloro-1-isopropyl-1H-pyrazole
4-chloro-1-isopropyl-1H-pyrazole
CAS:1205921-77-2
4-chloro-1-isopropyl-1H-pyrazole
2-Pyridinecarboxamide, N-(phenylmethoxy)-
2-Pyridinecarboxamide, N-(phenylmethoxy)-
CAS:663599-53-9
2-Pyridinecarboxamide, N-(phenylmethoxy)-
Propanamide, 2,2-dimethyl-N-phenyl-N-(phenylmethyl)-
Propanamide, 2,2-dimethyl-N-phenyl-N-(phenylmethyl)-
CAS:201550-70-1
Propanamide, 2,2-dimethyl-N-phenyl-N-(phenylmethyl)-
1-(2,2-dimethylpropanoyl)indoline
1-(2,2-dimethylpropanoyl)indoline
CAS:178809-22-8
1-(2,2-dimethylpropanoyl)indoline
3-iodo-1-[(4-methylphenyl)sulfonyl]-1H-Indole
3-iodo-1-[(4-methylphenyl)sulfonyl]-1H-Indole
CAS:170456-80-1
3-iodo-1-[(4-methylphenyl)sulfonyl]-1H-Indole
Carbamic acid, [2-(dimethylamino)-2-oxoethyl]-, phenylmethyl ester
Carbamic acid, [2-(dimethylamino)-2-oxoethyl]-, phenylmethyl ester
CAS:167303-60-8
Carbamic acid, [2-(dimethylamino)-2-oxoethyl]-, phenylmethyl ester
Carbamic acid, [(2-methoxyphenyl)methyl]-, 1,1-dimethylethyl ester
Carbamic acid, [(2-methoxyphenyl)methyl]-, 1,1-dimethylethyl ester
CAS:153903-20-9
Carbamic acid, [(2-methoxyphenyl)methyl]-, 1,1-dimethylethyl ester
4-METHYL-1-PROPAN-2-YLPYRAZOLE
4-METHYL-1-PROPAN-2-YLPYRAZOLE
CAS:130098-90-7
4-METHYL-1-PROPAN-2-YLPYRAZOLE
Boroxin, tris[4-(trifluoromethyl)phenyl]-
Boroxin, tris[4-(trifluoromethyl)phenyl]-
CAS:128796-45-2
Boroxin, tris[4-(trifluoromethyl)phenyl]-
HYDROXYLAMINE, O-[(2-BROMOPHENYL)METHYL]-
HYDROXYLAMINE, O-[(2-BROMOPHENYL)METHYL]-
CAS:107955-91-9
HYDROXYLAMINE, O-[(2-BROMOPHENYL)METHYL]-