Zhenhua Gu

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Name: 顾振华; ZhenHua Gu

Organization: University of Science and Technology of China , China

Department: Department of Chemistry

Title: Professor(PhD)

TOPICS

Organic Chemistry

Asymmetric Synthesis Amination

Chemicals
References

Synthesis of Chiral Cleft C,N-Palladium and Iridium Complexes from 2,3:6,7-Dibenzobicyclo[3.3.1]nona-2,6-diene-4,8-dione and Their Synthetic Applications

Co-reporter:Congfa He, Bin Wang, Mingli Gao, and Zhenhua Gu

Organometallics March 13, 2017 Volume 36(Issue 5) pp:1073-1073

Publication Date(Web):February 17, 2017

DOI:10.1021/acs.organomet.7b00024

A transition-metal-mediated functionalization of 2,3:6,7-dibenzobicyclo[3.3.1]nona-2,6-diene-4,8-dione is reported. By the use of the corresponding imine, iridium or palladium complexes were prepared, and they were well characterized by NMR and single-crystal X-ray crystallographic analysis. The catalytic activity of these two metal complexes was briefly investigated in hydrogenation and 1,2-addition reactions. Finally, the catalytic bromination of 2,3:6,7-dibenzobicyclo[3.3.1]nona-2,6-diene-4,8-dione was realized in the presence of NBS and Pd(OAc)2. Subsequently a new class of V-shaped molecules with biphenanthridine skeletons were synthesized.

Enantioselective Synthesis of Indole-Based Biaryl Atropisomers via Palladium-Catalyzed Dynamic Kinetic Intramolecular C–H Cyclization

Co-reporter:Congfa He, Mengqing Hou, Zixi Zhu, and Zhenhua Gu

ACS Catalysis August 4, 2017 Volume 7(Issue 8) pp:5316-5316

Publication Date(Web):July 11, 2017

DOI:10.1021/acscatal.7b01855

We report here a palladium-catalyzed enantioselective synthesis of indole-based atropisomers via an intramolecular dynamic kinetic C–H cyclization. The TADDOL-derived phosphoramidite ligand proves to be most efficient in this directing-group-free transformation, delivering products with up to 96:4 er. The thermal stability of the axial chirality of the atropisomers has also been investigated.Keywords: atropisomer; C−H cyclization; homogeneous catalysis; indole; palladium;

Synthesis of 2,3-dihydro-1H-phosphindole-1-oxides via the t-BuLi-mediated rearrangement of vinyl bromides and phosphine oxides

Co-reporter:Bin Li;Mingkai Zhang;Xulun Huang

Organic Chemistry Frontiers 2017 vol. 4(Issue 9) pp:1854-1857

Publication Date(Web):2017/08/22

DOI:10.1039/C7QO00310B

We report an intramolecular addition reaction of vinyllithium to phosphine oxides for the efficient synthesis of 2,3-dihydro-1H-phosphindole-1-oxides. Control experiments indicated that the reaction might proceed through an addition and concerted aryl migration process. The relative migration rate of aryl rings with different electronic properties was also briefly investigated.

Cleavage of the C(O)–S Bond of Thioesters by Palladium/Norbornene/Copper Cooperative Catalysis: An Efficient Synthesis of 2-(Arylthio)aryl Ketones

Co-reporter:Fenggang Sun; Miao Li; Congfa He; Bin Wang; Bin Li; Xianwei Sui

Journal of the American Chemical Society 2016 Volume 138(Issue 24) pp:7456-7459

Publication Date(Web):June 9, 2016

DOI:10.1021/jacs.6b02495

A Pd/norbornene/Cu cooperative catalysis for the efficient synthesis of 2-(arylthio)aryl ketones from aryl halides and thioesters has been developed. The first example of cooperative catalysis by palladium, norbornene, and copper, wherein the C(O)–S bond of thioesters is cleaved by a PdII palladacycle with the assistance of CuI, has been observed.

Total Synthesis of Aquatolide: Wolff Ring Contraction and Late-Stage Nozaki–Hiyama–Kishi Medium-Ring Formation

Co-reporter:Bin Wang, Yuanzhen Xie, Qin Yang, Guozhu Zhang, and Zhenhua Gu

Organic Letters 2016 Volume 18(Issue 20) pp:5388-5391

Publication Date(Web):October 5, 2016

DOI:10.1021/acs.orglett.6b02767

A total synthesis of the highly strained natural product aquatolide has been achieved. The synthesis featured a photoinduced Wolff ring contraction reaction for the construction of bicyclo[2.1.1]hexane from diazo compound with a bicyclo[2.2.1]heptane skeleton. The eight-membered enone was built by a late-stage intramolecular Nozaki–Hiyama–Kishi vinylation reaction of steric bulky vinyl iodide and aldehyde.

Catalytically Asymmetric Pd/Norbornene Catalysis: Enantioselective Synthesis of (+)-Rhazinal, (+)-Rhazinilam, and (+)-Kopsiyunnanine C1–3

Co-reporter:Kun Zhao, Shibo Xu, Chongqing Pan, Xianwei Sui, and Zhenhua Gu

Organic Letters 2016 Volume 18(Issue 15) pp:3782-3785

Publication Date(Web):July 12, 2016

DOI:10.1021/acs.orglett.6b01790

A catalytically asymmetric palladium/norbornene-catalyzed reaction is reported, where α-aryl tetrahydroquinoline derived phosphoramidite L15 is found to be the optimum ligand. Taking advantage of this transformation, the concise and unified enantioselective syntheses of (+)-rhazinal, (+)-rhazinilam, and (+)-kopsiyunnanine C1, C2, and C3 are realized.

Enantioselective Synthesis of Atropisomeric Vinyl Arene Compounds by Palladium Catalysis: A Carbene Strategy

Co-reporter:Jia Feng;Bin Li;Yun He ;Dr. Zhenhua Gu

Angewandte Chemie International Edition 2016 Volume 55( Issue 6) pp:2186-2190

Publication Date(Web):

DOI:10.1002/anie.201509571

Abstract

An efficient palladium-catalyzed asymmetric synthesis of axially chiral vinyl arenes from aryl bromides and hydrazones is reported. The products were easily oxidized to axially chiral biaryl compounds, and the phosphine oxides were readily reduced to phosphine ligands.

Enantioselective Synthesis of Atropisomeric Vinyl Arene Compounds by Palladium Catalysis: A Carbene Strategy

Co-reporter:Jia Feng;Bin Li;Yun He ;Dr. Zhenhua Gu

Angewandte Chemie 2016 Volume 128( Issue 6) pp:2226-2230

Publication Date(Web):

DOI:10.1002/ange.201509571

Abstract

Decarboxylative Alkynyl Termination of Palladium-Catalyzed Catellani Reaction: A Facile Synthesis of α-Alkynyl Anilines via Ortho C–H Amination and Alkynylation

Co-reporter:Fenggang Sun and Zhenhua Gu

Organic Letters 2015 Volume 17(Issue 9) pp:2222-2225

Publication Date(Web):April 22, 2015

DOI:10.1021/acs.orglett.5b00830

A palladium-catalyzed synthesis of α-alkynyl anilines is reported. The reaction proceeds via Catellani ortho C–H amination followed by decarboxylative alkynylative amination. Different terminal alkyne precursors were screened, and it was found that alkynyl carboxylic acids were superior over other alkynes, which led to operationally simple reaction conditions (no gradual addition of alkynes) and broad substrate scope. The reactivity of three different components matched well; as a result, relatively higher reaction temperature could be used, greatly shortening the reaction time to 4 h from the previously reported 144 h.

A Catalyst-Free Synthesis of Phosphinic Amides Using O-Benzoylhydroxylamines

Co-reporter:Rui Zhu, Chongqing Pan, and Zhenhua Gu

Organic Letters 2015 Volume 17(Issue 23) pp:5862-5865

Publication Date(Web):November 20, 2015

DOI:10.1021/acs.orglett.5b03056

A practical approach for the synthesis of phosphinic amides via the coupling of secondary phosphine oxides (SPOs) with O-benzoylhydroxylamines has been reported. Simply heating the mixture of SPOs and O-benzoylhydroxylamines in the presence of K2CO3 gave the phosphinic amides in moderate to excellent yields under an open air system. This method provides a practical and catalyst-free method for the synthesis of various synthetically valuable phosphinic amides.

Palladium-Catalyzed Catellani ortho-Acylation Reaction: An Efficient and Regiospecific Synthesis of Diaryl Ketones

Co-reporter:Yunze Huang;Rui Zhu;Kun Zhao ;Dr. Zhenhua Gu

Angewandte Chemie 2015 Volume 127( Issue 43) pp:12860-12863

Publication Date(Web):

DOI:10.1002/ange.201506446

Abstract

A palladium-catalyzed, norbornene-mediated Catellani ortho-acylation reaction was developed by the use of either acyl chlorides or acid anhydrides as acylation reagents. The addition of more than a stoichiometric amount of H₂O is crucial for this transformation when acid chlorides are used, and kinetic studies indicate that the active acylation reagent is possibly an acid anhydride.

Palladium-Catalyzed Heck-type Domino Cyclization and Carboxylation to Synthesize Carboxylic Acids by Utilizing Chloroform as the Carbon Monoxide Source

Co-reporter:Xianglei Liu, Bin Li, and Zhenhua Gu

The Journal of Organic Chemistry 2015 Volume 80(Issue 15) pp:7547-7554

Publication Date(Web):July 1, 2015

DOI:10.1021/acs.joc.5b01126

A palladium-catalyzed domino cyclization and carboxylation reaction for synthesis of a variety of carboxylic acids was developed, where chloroform was used as “carbon monoxide” source. The in situ generated neopentylpalladium species by Heck cyclization was efficiently trapped by dichlorocarbene to form a series of carboxylic acids. It was found that in this type of domino reaction CHCl3 is a convenient and safe alternation for CO gas.

BF3·OEt2-Promoted Synthesis of 2,3-Metallocenocyclohexanones: A 1,2-Hydride Shift and Cationic Cyclization Strategy

Co-reporter:Congfa He, Jie Wang, and Zhenhua Gu

The Journal of Organic Chemistry 2015 Volume 80(Issue 16) pp:7865-7875

Publication Date(Web):July 29, 2015

DOI:10.1021/acs.joc.5b01511

A BF3·OEt2-promoted cyclization of metallocenyl enones to form cyclohexanone-fused metallocenes is reported. 2,3-Metallocenocyclohexanones were formed exclusively, and no normal Nazarov-type cyclopentanone analogues were detected. The reaction possibly proceeded via an unusual cationic 1,2-hydride shift followed by Friedel–Crafts alkylative cyclization process. During the studies of the alkylation reaction of these keto esters, an unusual and rare facial selectivity was observed. The electrophiles would be attacked from the same face as the second Cp ring.

Palladium-Catalyzed Catellani ortho-Acylation Reaction: An Efficient and Regiospecific Synthesis of Diaryl Ketones

Co-reporter:Yunze Huang;Rui Zhu;Kun Zhao ;Dr. Zhenhua Gu

Angewandte Chemie International Edition 2015 Volume 54( Issue 43) pp:12669-12672

Publication Date(Web):

DOI:10.1002/anie.201506446

Abstract

Palladium-Catalyzed Intramolecular Asymmetric C–H Functionalization/Cyclization Reaction of Metallocenes: An Efficient Approach toward the Synthesis of Planar Chiral Metallocene Compounds

Co-reporter:Ruixian Deng ; Yunze Huang ; Xinna Ma ; Gencheng Li ; Rui Zhu ; Bin Wang ; Yan-Biao Kang

Journal of the American Chemical Society 2014 Volume 136(Issue 12) pp:4472-4475

Publication Date(Web):March 11, 2014

DOI:10.1021/ja500699x

A palladium-catalyzed asymmetric synthesis of planar chiral metallocene compounds is reported. The reaction stereoselectively functionalized one of the ortho C–H bonds of Cp rings by intramolecular cyclization to form indenone derivatives in high yields with excellent enantioselectivity. The mild set of reaction conditions allowed a wide variety of chiral metallocene compounds to be synthesized with broad functional group tolerance. The influences of preinstalled chiralities on the other Cp-ring were also investigated.

N-Bromoacetamide-mediated domino cyclization and elimination of homoallylic trichloroacetimidates: a novel approach toward the synthesis of 1-bromo-2-amino-3-butene derivatives

Co-reporter:Rui Zhu, Kai Yu and Zhenhua Gu

Organic & Biomolecular Chemistry 2014 vol. 12(Issue 34) pp:6653-6660

Publication Date(Web):03 Jul 2014

DOI:10.1039/C4OB01126K

A practical synthesis of 1-bromo-2-amino-3-butene derivatives from homoallylic trichloroacetimidates was reported. Simply heating the mixture of substrates and N-bromoacetamide in DMF at 90 °C would give the desired products in moderate to excellent yields. The reaction may proceed through a domino bromo-cyclization and elimination pathway. The synthesis of 4,5-dihydrooxazoles from 1-bromo-2-amino-3-butene derivatives was also investigated.

Palladium-catalyzed intramolecular Cp–H bond functionalization/arylation: an enantioselective approach to planar chiral quinilinoferrocenes

Co-reporter:Xinna Ma and Zhenhua Gu

RSC Advances 2014 vol. 4(Issue 68) pp:36241-36244

Publication Date(Web):11 Aug 2014

DOI:10.1039/C4RA07832B

A palladium-catalyzed intramolecular asymmetric Cp–H functionalization/cyclization reaction to construct planar chiral quinilinoferrocenes was reported. The current investigation indicated that Carriera's O-PINAP ligands gave the best enantiomeric induction. The palladium-catalyzed reaction allowed a variety of chiral quinilinoferrocenes to be synthesized with broad functional group tolerance.

Stereoselective Synthesis of 1,3-Amino Alcohols by the Pd-Catalyzed Cyclization of Trichloroacetimidates

Co-reporter:Yuanzhen Xie, Kai Yu, and Zhenhua Gu

The Journal of Organic Chemistry 2014 Volume 79(Issue 3) pp:1289-1302

Publication Date(Web):January 14, 2014

DOI:10.1021/jo402681z

The synthesis of 4-vinyl-5,6-dihydro-1,3-oxazines, precursors of 1,3-amino alcohols, using the palladium-catalyzed cyclization of trichloroacetimidates is reported. The reaction favors the formation of the 4,6-cis-isomers with up to >20:1 diastereoselectivity. Chemoselective hydrolysis of the resulting 5,6-dihydro-1,3-oxazines was also investigated.

Pd-Catalyzed Chemoselective Catellani Ortho-Arylation of Iodopyrroles: Rapid Total Synthesis of Rhazinal

Co-reporter:Xianwei Sui ; Rui Zhu ; Gencheng Li ; Xinna Ma

Journal of the American Chemical Society 2013 Volume 135(Issue 25) pp:9318-9321

Publication Date(Web):June 11, 2013

DOI:10.1021/ja404494u

A Pd-catalyzed chemoselective Catellani reaction of iodopyrroles was developed. The rare chemoselectivity between two different aryl halides was realized by optimizing the kinetics of the different steps of this multicomponent process. The new developed method led to the rapid synthesis of rhazinal in a highly efficient manner.

Pd-Catalyzed Heck-Type Cascade Reactions with N-Tosyl Hydrazones: An Efficient Way to Alkenes via in Situ Generated Alkylpalladium

Co-reporter:Xianglei Liu, Xinna Ma, Yunze Huang, and Zhenhua Gu

Organic Letters 2013 Volume 15(Issue 18) pp:4814-4817

Publication Date(Web):September 9, 2013

DOI:10.1021/ol402210a

A palladium-catalyzed Heck-type cascade reaction of aryl halides and N-tosyl hydrazones is reported. The neopentylpalladium species, generated from an intramolecular Heck-type insertion reaction of aryl halides, could efficiently react with carbenes to form highly functionalized alkenes. The synthesis of spiro compounds was also explored via a multiple Heck-type insertion reaction with N-tosyl hydrazone.

N-Bromoacetamide-mediated domino cyclization and elimination of homoallylic trichloroacetimidates: a novel approach toward the synthesis of 1-bromo-2-amino-3-butene derivatives

Co-reporter:Rui Zhu, Kai Yu and Zhenhua Gu

Organic & Biomolecular Chemistry 2014 - vol. 12(Issue 34) pp:NaN6660-6660

Publication Date(Web):2014/07/03

DOI:10.1039/C4OB01126K

The palladium/norbornene-catalyzed ortho-silylmethylation reaction: a practical protocol for ortho-functionalized one-carbon homologation of aryl iodides

Co-reporter:Xianwei Sui, Linlin Ding and Zhenhua Gu

Chemical Communications 2016 - vol. 52(Issue 97) pp:NaN14002-14002

Publication Date(Web):2016/11/10

DOI:10.1039/C6CC08227K

A palladium/norbornene-catalyzed ortho-silylmethylation reaction using of (iodomethyl)cyclohexyloxydimethylsilane as the electrophile was reported. The ((cyclohexyloxy)dimethylsilyl)methyl group was readily oxidized using the Fleming–Tamao process or by ceric ammonium nitrate to give benzylic alcohol derivatives. This method was successfully applied in a concise synthesis of a biaryl analogue of schisandrins.

Pd/norbornene-catalyzed sequential ortho-C–H alkylation and ipso-alkynylation: a 1,1-dimethyl-2-alkynol strategy

Co-reporter:Fenggang Sun, Miao Li and Zhenhua Gu

Inorganic Chemistry Frontiers 2016 - vol. 3(Issue 3) pp:

Publication Date(Web):

DOI:10.1039/C5QO00391A

Pd-catalyzed Heck cyclization and in situ hydrocarboxylation or hydromethenylation via a hydrogen borrowing strategy

Co-reporter:Xianglei Liu and Zhenhua Gu

Inorganic Chemistry Frontiers 2015 - vol. 2(Issue 7) pp:NaN782-782

Publication Date(Web):2015/04/28

DOI:10.1039/C5QO00091B

A Pd-catalyzed hydrocarboxylation of the in situ formed neopentylic alkenes by the use of “borrowed hydrogen” from Heck-type β-hydride elimination was reported. The advantage of this strategy is that no additional hydrogen sources or organometallic reagents were required. It was found that CHCl3 was not only used as a safe and convenient “CO” source but also proved superior in the linear/branched selectivity over carbon monoxide. Furthermore, the in situ formed neopentylic alkenes could be chemoselectively functionalized with other C–C unsaturated bonds being unchanged, even the less sterically hindered ones.

Highly efficient and practical resolution of 2,3:6,7-dibenzobicyclo[3.3.1]nona-2,6-diene-4,8-dione and stereoselective synthesis of its chiral diamine derivatives

Co-reporter:Bin Wang and Zhenhua Gu

Inorganic Chemistry Frontiers 2014 - vol. 1(Issue 3) pp:NaN274-274

Publication Date(Web):2014/02/26

DOI:10.1039/C4QO00011K

Highly efficient and practical resolution of 2,3:6,7-dibenzobicyclo[3.3.1]nona-2,6-diene-4,8-dione by inclusion complexation with commercially available enantiopure 1,1′-bi-2-naphthol is reported. The structure of the 1:1 inclusion complex of the diketone and BINOL was confirmed by single crystal X-ray crystallography.