Gang Zou

Name: 邹刚; Zou, Gang

Organization: East China University of Science and Technology , China

Department: Laboratory of Advanced Materials and Institute of Fine Chemicals

Title: Professor(PhD)

Chemicals
References

Bifunctional Quaternary Ammonium Salts Catalyzed Stereoselective Conjugate Addition of Oxindoles to Electron-Deficient β-Haloalkenes

Co-reporter:Qiaowen Jin, Changwu Zheng, Gang Zhao, and Gang Zou

The Journal of Organic Chemistry May 5, 2017 Volume 82(Issue 9) pp:4840-4840

Publication Date(Web):April 14, 2017

DOI:10.1021/acs.joc.7b00571

A highly Z-selective asymmetric conjugate addition of 3-substituted oxindoles to β-haloalkene ketones/esters catalyzed by readily available chiral bifunctional quaternary ammonium salts is reported. This reaction provides efficient access to a range of 2-oxoindole derivatives bearing a thermodynamically unstable Z-olefin structure and a chiral quaternary carbon center in high yields (up to 90%) and with good to high stereoselectivities (up to >19:1 Z/E and 91% ee) under mild conditions.

Base-assisted, copper-catalyzed N-arylation of (benz)imidazoles and amines with diarylborinic acids

Co-reporter:Changwei Guan, Yuanyuan Feng, Gang Zou, Jie Tang

Tetrahedron 2017 Volume 73, Issue 49(Issue 49) pp:

Publication Date(Web):7 December 2017

DOI:10.1016/j.tet.2017.10.043

N-Arylation of (benz)imidazoles and amines with diarylborinic acids as cost-effective aryl source has been efficiently effected via Cu(OAc)2-catalyzed Chan-Lam coupling in assistance of tetramethylethylenediamine (TMEDA) in methanol and pyridine (Py) in dichloromethane, respectively, in air at room temperature. The diarylborinic acids could be well accommodated by the Chan-Lam coupling oxidative conditions containing a proper combination of bases and solvents. The steric hindrance appeared to affect the copper-catalyzed N-arylation using the high-order arylboron reagent more significantly than the electronic factors, especially for low reactive anilines and aliphatic amines.Download high-res image (99KB)Download full-size image

A Sequential Suzuki Coupling Approach to Unsymmetrical Aryl s-Triazines from Cyanuric Chloride

Co-reporter:Chen Wang;Jiehui Zhang;Jie Tang

Advanced Synthesis & Catalysis 2017 Volume 359(Issue 14) pp:2514-2519

Publication Date(Web):2017/07/17

DOI:10.1002/adsc.201700260

AbstractA practical approach has been developed for efficient synthesis of unsymmetrical aryl s-triazines via highly selective sequential Suzuki coupling of cyanuric chloride (2,4,6-trichlorotriazine) with aryl or vinyl boronic or diarylborinic acids catalysed by 0.1–0.5 mol% Pd(PPh3)2Cl2 under mild conditions. The second and third Suzuki couplings for unsymmetrically trisubstituted aryl s-triazines could be more practically conducted in one-pot procedure. An electron-withdrawing conjugate group at phenyl ring of arylboronic acids was unexpectedly found to completely block the coupling while steric hindrance from an ortho electron-donating substituent could be overcome.

Palladium-catalyzed cross-coupling of aryl chlorides with O, N-chelate stabilized diarylborinates

Co-reporter:Nan Zhang, Chen Wang, Gang Zou, Jie Tang

Journal of Organometallic Chemistry 2017 Volume 842(Volume 842) pp:

Publication Date(Web):1 August 2017

DOI:10.1016/j.jorganchem.2017.05.013

•O, N-chelate stabilized diarylborinates prepared and fully characterized.•Cross-coupling of aryl chlorides with O, N-chelate stabilized diarylborinates achieved.•A six-membered O, N-chelate to B balances the stability and reactivity of diarylborinates.•Structural effects from both aryl chlorides and diarylborinates investigated.A series of O, N-chelated diarylborinates have been prepared and tested as arylboron counterpart alternative to oxygen-labile diarylborinic acids in palladium catalyzed Suzuki coupling of aryl chlorides. 3-Dimethylaminopropyl diarylborinates (B-5a), featuring a six-membered O, N-chelated boron ring that was confirmed by single crystal X-ray diffraction, displayed a delicately balanced stability and reactivity. Their cross-coupling with structurally various aryl chlorides could be effected as efficiently as that of the parent diarylborinic acids by using 0.1∼1mol% Pd(OAc)2/IPr/P(OPh)3 as catalyst system, to provide the corresponding biaryls in good to excellent yields.Download high-res image (119KB)Download full-size image

Dipeptide-derived multifunctional phosphonium salt as a catalyst to synthesize highly functionalized chiral cyclopentanes

Co-reporter:Yingpeng Lu, Dongdong Cao, Jiaxing Zhang, Hongyu Wang, Gang Zou, Gang Zhao

Tetrahedron 2016 Volume 72(27–28) pp:4141-4150

Publication Date(Web):7 July 2016

DOI:10.1016/j.tet.2016.05.065

Asymmetric tandem Michael–Michael reactions between 2-substituted malonates and low reactive enones have been achieved by using novel dipeptides-derived phosphonium salts, affording the synthetically useful and highly functionalized chiral cyclopentanes with good yields, diastereoselectivities and high enantioselectivities.

Palladium-Catalyzed Room-Temperature Acylative Suzuki Coupling of High-Order Aryl Borons with Carboxylic Acids

Co-reporter:Shufen Si, Chen Wang, Nan Zhang, and Gang Zou

The Journal of Organic Chemistry 2016 Volume 81(Issue 10) pp:4364-4370

Publication Date(Web):April 21, 2016

DOI:10.1021/acs.joc.6b00421

This note describes a dimethyl dicarbonate-assisted, Pd(OAc)2/PPh3-catalyzed acylative Suzuki coupling of carboxylic acids with diarylborinic acids or tetraarylboronates for practical and efficient synthesis of sterically undemanding aryl ketones at room temperature. More than just cost-effective alternatives to aryl boronic acids, diarylborinic acids and tetraarylboronates displayed higher reactivity in the acylative Suzuki coupling. A variety of alkyl aryl ketones, including those bearing a hydroxy, bromo, or carbonyl group, could be readily obtained in modest to excellent yields.

Acylative Suzuki coupling of amides: acyl-nitrogen activation via synergy of independently modifiable activating groups

Co-reporter:Xijing Li and Gang Zou

Chemical Communications 2015 vol. 51(Issue 24) pp:5089-5092

Publication Date(Web):17 Feb 2015

DOI:10.1039/C5CC00430F

A highly efficient palladium-catalyzed acylative cross-coupling of carboxylic amides with arylboronic acids has been achieved via synergistic activation of the Cacyl–N bond by independently modifiable activating groups. Coupling of amides features not only good functional group tolerance but also modifiable reactivities to overcome steric hindrance.

Primary-secondary diamines catalyzed Michael reaction to generate chiral fluorinated quaternary carbon centers

Co-reporter:Yingpeng Lu, Gang Zou, Gang Zhao

Tetrahedron 2015 Volume 71(Issue 24) pp:4137-4144

Publication Date(Web):17 June 2015

DOI:10.1016/j.tet.2015.04.103

Asymmetric Michael reactions of α-fluoro-β-ketoesters to nitroolefins have been achieved by using readily accessible primary-secondary diamines as the organocatalysts through enamine activation mode, affording the useful Michael adducts bearing chiral fluorinated quaternary carbon in good yields, with high diastereoselectivities and enantioselectivities (up to 87% yield, >20:1 d.r. and 99% ee).

N-Heterocyclic carbene/phosphite synergistically assisted Pd/C-catalyzed Suzuki coupling of aryl chlorides

Co-reporter:Haihua Ke;Xiaofeng Chen

Applied Organometallic Chemistry 2014 Volume 28( Issue 1) pp:54-60

Publication Date(Web):

DOI:10.1002/aoc.3076

An N-heterocyclic carbene and phosphite synergistically enhanced Pd/C catalyst system has been developed for Suzuki coupling of aryl chlorides and aryl boronic acids from commercially available Pd/C with sterically demanding N,N′-bis(2,6-diisopropylphenyl)imidazolylidene and trimethylphosphite. A remarkable increase in catalytic activity of Pd/C was observed when used along with 1 equiv. N,N′-bis(2,6-diisopropylphenyl)imidazolium chloride and 2 equiv. phosphite with respect to palladium in appropriate solvents that were found to play a crucial role in Pd/C-NHC-P(OR)₃-catalyzed Suzuki coupling. A dramatic ortho-substitution effect of carbonyl and nitrile groups in aryl chlorides was observed and explained by a modified quasi-heterogeneous catalysis mechanism. The Pd/C catalyst could be easily recovered from reaction mixtures by simple filtration and only low palladium contamination was detected in the biparyl products. A practical process for the synthesis of 4-biphenylcarbonitrile has therefore been developed using the N-heterocyclic carbene/phosphite-assisted Pd/C-catalyzed Suzuki coupling. Copyright © 2013 John Wiley & Sons, Ltd.

N-Heterocyclic Carbene-Assisted, Bis(phosphine)nickel-Catalyzed Cross-Couplings of Diarylborinic Acids with Aryl Chlorides, Tosylates, and Sulfamates

Co-reporter:Haihua Ke, Xiaofeng Chen, and Gang Zou

The Journal of Organic Chemistry 2014 Volume 79(Issue 15) pp:7132-7140

Publication Date(Web):July 15, 2014

DOI:10.1021/jo501291y

Efficient bis(phosphine)nickel-catalyzed cross-couplings of diarylborinic acids with aryl chlorides, tosylates, and sulfamates have been effected with an assistance of N-heterocyclic carbene (NHC) generated in situ from N,N′-dialkylimidazoliums, e.g., N-butyl-N′-methylimidazolium bromide ([Bmim]Br), in toluene using K3PO4·3H2O as base. In contrast to bis(NHC)nickel-catalyzed conventional Suzuki coupling of arylboronic acids, mono(NHC)bis(phosphine)nickel species generated in situ from Ni(PPh3)2Cl2/[Bmim]Br displayed high catalytic activities in the cross-couplings of diarylborinic acids. The structural influences from diarylborinic acids were found to be rather small, while electronic factors from aryl chlorides, tosylates, and sulfamates affected the couplings remarkably. The couplings of electronically activated aryl chlorides, tosylates, and sulfamates could be efficiently effected with 1.5 mol % NiCl2(PPh3)2/[Bmim]Br as catalyst precursor to give the biaryl products in excellent yields, while 3–5 mol % loadings had to be used for the couplings of non- and deactivated ones. A small ortho-substitutent on the aromatic ring of aryl chlorides, tosylates, and sulfamates was tolerable. Applicability of the nickel-catalyzed cross-couplings in practical synthesis of fine chemicals has been demonstrated in process development for a third-generation topical retinoid, Adapalene.

Highly efficient nickel/phosphine catalyzed cross-couplings of diarylborinic acids with aryl tosylates and sulfamates

Co-reporter:HaiHua Ke;XiaoFeng Chen;YuanYuan Feng

Science China Chemistry 2014 Volume 57( Issue 8) pp:1126-1131

Publication Date(Web):2014 August

DOI:10.1007/s11426-014-5138-3

Highly efficient cross-couplings of diarylborinic acids with aryl tosylates and sulfamates are reported for construction of biaryls using a tri(4-methoxyphenyl)phosphine-supported nickel catalyst system: Ni[P(4-MeOC6H4)3]2Cl2/2P(4-MeOC6H4)3 in the presence of K3PO4·3H2O in toluene. A variety of unsymmetrical biaryls could be obtained in good to excellent yields with 1.5–3 mol% or 3–5 mol% catalyst loadings for aryl sulfamates and tosylates, respectively. In sharp contrast to the conventional nickel-catalyzed Suzuki coupling with arylboronic acids, arylsulfamates unexpectedly displayed a higher reactivity than the corresponding tosylates in coupling with diarylborinic acids catalyzed by the nickel/phosphine catalyst system.

Asymmetric Intramolecular Oxa-Michael Reactions to Tetrahydrofurans/2H-Pyrans Catalyzed by Primary–Secondary Diamines

Co-reporter:Yingpeng Lu, Gang Zou, and Gang Zhao

ACS Catalysis 2013 Volume 3(Issue 6) pp:1356

Publication Date(Web):May 16, 2013

DOI:10.1021/cs4002332

The asymmetric intramolecular oxa-Michael reactions of α,β-unsaturated ketones have been achieved by using readily accessible primary–secondary diamines as the organocatalysts, giving the synthetically useful tetrahydrofurans/2H-pyrans in good yields and with high enantioselectivities (up to 90% ee).Keywords: asymmetric catalysis; diamine catalyst; organocatalysis; oxa-Michael reaction; tetrahydrofurans

Synthesis of Diarylmethanes via Metal-Free Reductive Cross-Coupling of Diarylborinic Acids with Tosyl Hydrazones

Co-reporter:Xijing Li, Yuanyuan Feng, Lin Lin, and Gang Zou

The Journal of Organic Chemistry 2012 Volume 77(Issue 23) pp:10991-10995

Publication Date(Web):November 12, 2012

DOI:10.1021/jo302207b

This paper describes a practical and efficient procedure that takes advantage of diarylborinic acids as a cost-effective alternative to arylboronic acids for synthesis of diarylmethanes through metal-free reductive cross-coupling with N-tosylhydrazones of aromatic aldehydes and ketones. The procedure tolerates hydroxyl, halide, amine, and allyl functionality, complementary to the transition-metal catalyzed cross-coupling techniques.

Cross-Coupling of Diarylborinic Acids and Anhydrides with Arylhalides Catalyzed by a Phosphite/N-Heterocyclic Carbene Co-supported Palladium Catalyst System

Co-reporter:Xiaofeng Chen, Haihua Ke, Yao Chen, Changwei Guan, and Gang Zou

The Journal of Organic Chemistry 2012 Volume 77(Issue 17) pp:7572-7578

Publication Date(Web):August 6, 2012

DOI:10.1021/jo301335x

A highly efficient cross-coupling of diarylborinic acids and anhydrides with aryl chlorides and bromides has been effected by using a palladium catalyst system co-supported by a strong σ-donor N-heterocyclic carbene (NHC), N,N′-bis(2,6-diisopropylphenyl) imidazol-2-ylidene, and a strong π-acceptor phosphite, triphenylphosphite, in tert-BuOH in the present of K3PO4·3H2O. Unsymmetrical biaryls with a variety of functional groups could be obtained in good to excellent yields using as low as 0.01, 0.2–0.5, and 1 mol % palladium loadings for aryl bromides and activated and deactivated aryl chlorides, respectively, under mild conditions. A ligand synergy between the σ-donor NHC and the π-acceptor phosphite in the Pd/NHC/P(OPh)3 catalytic system has been proposed to be responsible for the high efficacy to arylchlorides in the cross-coupling. A scalable and economical process has therefore been developed for synthesis of Sartan biphenyl from the Pd/NHC/P(OPh)3 catalyzed cross-coupling of di(4-methylphenyl)borinic acid with 2-chlorobenzonitrile.

Tunable protic ionic liquids as solvent-catalysts for improved synthesis of multiply substituted 1,2,4-triazoles from oxadiazoles and organoamines

Co-reporter:Xiaofeng Chen, Rui Liu, Yuan Xu, Gang Zou

Tetrahedron 2012 68(24) pp: 4813-4819

Publication Date(Web):

DOI:10.1016/j.tet.2012.03.114

Highly Enantioselective Epoxidation of ,-Unsaturated Ketones Catalyzed by Primary-Secondary Diamines

Co-reporter:Yingpeng Lu;Changwu Zheng;Yingquan Yang;Gang Zhao

Advanced Synthesis & Catalysis 2011 Volume 353( Issue 17) pp:3129-3133

Publication Date(Web):

DOI:10.1002/adsc.201100230

Abstract

The asymmetric epoxidation of α,β-unsaturated ketones has been achieved by using functional and readily accessible primary-secondary diamines as the catalysts, giving the useful alkyl epoxy products with good yields and high enantioselectivities (up to 99% ee).

Well-defined N-heterocyclic carbene silver halides of 1-cyclohexyl-3-arylmethylimidazolylidenes: synthesis, structure and catalysis in A3-reaction of aldehydes, amines and alkynes

Co-reporter:Yanbo Li, Xiaofeng Chen, Yin Song, Ling Fang and Gang Zou

Dalton Transactions 2011 vol. 40(Issue 9) pp:2046-2052

Publication Date(Web):24 Jan 2011

DOI:10.1039/C0DT01074J

Structurally well-defined N-heterocyclic carbene silver chlorides and bromides supported by 1-cyclohexyl-3-benzylimidazolylidene (CyBn-NHC) or 1-cyclohexyl-3-naphthalen-2-ylmethylimidazolylidene (CyNaph-NHC) were synthesized by reaction of the corresponding imidazolium halides with silver(I) oxide while cationic bis(CyBn-NHC) silver nitrate was isolated under similar conditions using imidazolium iodide in the presence of sodium nitrate. Single-crystal X-ray diffraction revealed a dimeric structure through a nonpolar weak-hydrogen-bond supported Ag–Ag bond for 1-cyclohexyl-3-benzylimidazolylidene silver halides [(CyBn-NHC)AgX]2 (X = Cl, 1; Br, 2) but a monomeric structure for N-heterocyclic carbene silver halides with the more sterically demanding 1-cyclohexyl-3-naphthalen-2-ylmethylimidazolylidene ligand (CyNaph-NHC)AgX (X = Cl, 4; Br, 5). Cationic biscarbene silver nitrate [(CyBn-NHC)2Ag]+NO3−3 assumed a cis orientation with respect to the two carbene ligands. The monomeric complexes (CyNaph-NHC)AgX 4 and 5 showed higher catalytic activity than the dimeric [(CyBn-NHC)AgX]21 and 2 as well as the cationic biscarbene silver nitrate 3 in the model three component reaction of 3-phenylpropionaldehyde, phenylacetylene and piperidine with chloride 4 performing best and giving product in almost quantitative yield within 2 h at 100 °C. An explanation for the structure–activity relationship in N-heterocyclic carbene silver halide catalyzed three component reaction is given based on a slightly modified mechanism from the one in literature.

Single, double and triple deprotonation of a β-diketimine bearing pendant pyridyl group and the corresponding rare-earth metal complexes

Co-reporter:Xin Xu, Yaofeng Chen, Gang Zou and Jie Sun

Dalton Transactions 2010 vol. 39(Issue 16) pp:3952-3958

Publication Date(Web):16 Mar 2010

DOI:10.1039/B926898G

A new β-diketimine bearing the pendant pyridyl group, CH3C(2,6-(iPr)2C6H3NH)CHC(CH3)(NCH2–C5NH4) (L1), was synthesized. The reaction of L1 with one equivalent of Sc(CH2SiMe3)3(THF)2 at room temperature gave a singly deprotonated product (L1−H)Sc(CH2SiMe3)2 (1). Y(CH2SiMe3)3(THF)2 under the same conditions led to the unexpected dimer [(L1−H3)Y(THF)]2 (2), in which the ligand precursor L1 was triply deprotonated. The reaction of L1 with Y(CH2SiMe3)3(THF)2 at −35 °C provided a mixture of singly deprotonated product (L1−H)Y(CH2SiMe3)2 (3) and doubly deprotonated product (L1−H2)Y(CH2SiMe3)(THF)2 (4). The reactions of L1 with Ln[N(SiMe3)2]3 gave only singly deprotonated products (L1−H)Ln[N(SiMe3)2]2 (5: Ln = Y; 6: Ln = La). The complexes 1, 2 and 4–6 have been characterized by single-crystal X-ray diffraction.

Hemilabile-coordinated copper promoted amination of aryl halides with ammonia in aqueous ethylene glycol under atmosphere pressure

Co-reporter:Zhennü Guo;Jiayi Guo;Ying Song;Limin Wang

Applied Organometallic Chemistry 2009 Volume 23( Issue 4) pp:150-153

Publication Date(Web):

DOI:10.1002/aoc.1485

Abstract

Direct amination of aryl iodides and bromides with ammonia under 1 atm pressure has been effected using in situ-generated hemilabile coordinated copper(I) species from copper(I) halides or copper metal in aqueous ethylene glycol, producing primary aromatic amines in good yields. Ammonia pressure and water were found to accelerate the copper-mediated reaction while strong chelating ligands showed a suppression effect. A rationale for the copper-mediated amination of aryl halides with ammonia is given based on a double-face role of chelating effect. Copyright © 2009 John Wiley & Sons, Ltd.

Baylis–Hillman reaction promoted by a recyclable protic-ionic-liquid solvent–catalyst system: DABCO–AcOH–H2O

Co-reporter:Ying Song, Haihua Ke, Nan Wang, Limin Wang, Gang Zou

Tetrahedron 2009 65(45) pp: 9086-9090

Publication Date(Web):

DOI:10.1016/j.tet.2009.09.049

Heck-type coupling vs. conjugate addition in phosphine–rhodium catalyzed reactions of aryl boronic acids with α,β-unsaturated carbonyl compounds: a systematic investigation

Co-reporter:Gang Zou, Jianping Guo, Zhiyong Wang, Wen Huang and Jie Tang

Dalton Transactions 2007 (Issue 28) pp:3055-3064

Publication Date(Web):14 May 2007

DOI:10.1039/B615473E

The competition between Heck-type coupling and conjugate addition in phosphine–rhodium catalyzed reactions of aryl boronic acids with α,β-unsaturated carbonyls has been systematically investigated in a toluene–H2O biphasic system. Aside from the intrinsic nature of rhodium and the enolization of carbonyls, the phosphine supporting ligand on rhodium, the ratio of aryl boronic acid to α,β-unsaturated carbonyl and the pH value of the aqueous phase were found to affect the competition significantly. Highly selective rhodium-based catalyst systems have therefore been developed for both Heck-type coupling and conjugate addition by synergistically tuning the supporting ligand, the boronic acid to olefin ratio and other reaction conditions. Conjugate addition with selectivity >99% and Heck-type coupling with selectivity of up to 100%, 98% and 84% for acrylates, acrylamides and methyl vinyl ketone, respectively, could be achieved in the rhodium-catalyzed reactions of aryl boronic acids with α,β-unsaturated carbonyls using the corresponding optimized rhodium-based catalyst systems.

Heck-type coupling vs. conjugate addition in phosphine–rhodium catalyzed reactions of aryl boronic acids with α,β-unsaturated carbonyl compounds: a systematic investigation

Co-reporter:Gang Zou, Jianping Guo, Zhiyong Wang, Wen Huang and Jie Tang

Dalton Transactions 2007(Issue 28) pp:

Publication Date(Web):

DOI:10.1039/B615473E

Single, double and triple deprotonation of a β-diketimine bearing pendant pyridyl group and the corresponding rare-earth metal complexes

Co-reporter:Xin Xu, Yaofeng Chen, Gang Zou and Jie Sun

Dalton Transactions 2010 - vol. 39(Issue 16) pp:NaN3958-3958

Publication Date(Web):2010/03/16

DOI:10.1039/B926898G

Acylative Suzuki coupling of amides: acyl-nitrogen activation via synergy of independently modifiable activating groups

Co-reporter:Xijing Li and Gang Zou