Yue-ming Li

Name:

Organization: Nankai University

Department: College of Pharmacy and Tianjin Key Laboratory of Molecular Drug Research

Title:

Chemicals
References

Intramolecular Aminoalkoxylation of Unfunctionalized Olefins via Intramolecular Iodoamination and Aziridinium Ion Ring-Opening Sequence

Co-reporter:Hui Sun, Bin Cui, Lili Duan, and Yue-Ming Li

Organic Letters April 7, 2017 Volume 19(Issue 7) pp:

Publication Date(Web):March 23, 2017

DOI:10.1021/acs.orglett.7b00284

The preparation of prolinol ether type compounds was realized via MnI2-catalyzed intramolecular iodoamination of unfunctionalized olefins and subsequent ring opening of an aziridinium ion intermediate with alcohols/phenols. In the presence of a catalytic amount of MnI2 and 2 equiv of NaI, intramolecular aminoalkoxylation of different N-benzyl-5-methylhex-4-en-1-amine substrates proceeded readily in alcoholic solvents, leading to 2-(alkoxyalkyl)pyrrolidine products in up to 90% isolated yields.

MgCl2-catalyzed trifluoromethylation of carbonyl compounds using (trifluoromethyl)trimethylsilane as the trifluoromethylating agent

Co-reporter:Bin Cui, Hui Sun, Yibo Xu, Lili Duan, Yue-Ming Li

Tetrahedron 2017 Volume 73, Issue 48(Issue 48) pp:

Publication Date(Web):30 November 2017

DOI:10.1016/j.tet.2017.10.021

Using (trifluoromethyl)trimethylsilane (TMSCF3) as the trifluoromethylating agent, MgCl2-catalyzed trifluoromethylation of carbonyl compounds proceeded readily at room temperature. In the presence of 10 mol% of MgCl2, a variety of carbonyl substrates such as aliphatic/aromatic aldehydes, acyclic/cyclic ketones and esters could be trifluoromethylated in DMF, giving the corresponding trimethylsilyl ethers (ketals) in up to 93% isolated yields. Trifluoromethylketones could be readily obtained after hydrolysis of the trimethylsilyl ketals. The reactions could tolerate air and moisture, and the use of oxygen and moisture-free conditions was not required.Download high-res image (180KB)Download full-size image

CuBr2-promoted intramolecular bromocyclization of N-allylamides and aryl allyl ketone oximes

Co-reporter:Chun-Hua Yang, Zhong-Qi Xu, Lili Duan, Yue-Ming Li

Tetrahedron 2017 Volume 73, Issue 48(Issue 48) pp:

Publication Date(Web):30 November 2017

DOI:10.1016/j.tet.2017.10.025

A new and easy-to-perform route to 2-oxazolines amd isoxazolines was reported. Using CuBr2 as both the bromide source and the reaction promoter, bromocyclization of N-allylamides and allyl ketone oximes proceeded readily, leading to oxazolines and isoxazolines in good to excellent yields.Download high-res image (87KB)Download full-size image

Preparation of trans-2-Substituted-4-halopiperidines and cis-2-Substituted-4-halotetrahydropyrans via AlCl3-Catalyzed Prins Reaction

Co-reporter:Gong-Qing Liu, Bin Cui, Rong Xu, and Yue-Ming Li

The Journal of Organic Chemistry 2016 Volume 81(Issue 12) pp:5144-5161

Publication Date(Web):May 23, 2016

DOI:10.1021/acs.joc.6b00725

A general and practical method for the preparation of trans-2-substituted-4-halopiperidines and cis-2-substituted-4-halotetrahydropyrans is reported. Using 5 mol % of AlCl3 as the catalyst and 2 equiv of trimethylsilyl halides as the halide sources, aza-Prins cyclization of N-tosyl homoallylamine or Prins cyclization of homoallylic alcohol with carbonyl compounds could be readily realized, giving the corresponding trans-2-substituted-4-halopiperidines or cis-2-substituted-4-halotetrahydropyrans in high yields and satisfactory diastereoselectivity.

MnI2-catalyzed regioselective intramolecular iodoamination of unfunctionalized olefins

Co-reporter:Hui Sun, Bin Cui, Gong-Qing Liu, Yue-Ming Li

Tetrahedron 2016 Volume 72(Issue 45) pp:7170-7178

Publication Date(Web):10 November 2016

DOI:10.1016/j.tet.2016.09.038

MnI2-catalyzed intramolecular iodoamination of unfunctionalized olefins was reported. Interaction of MnI2 with N-alkenyl amine/sulfonamide gave NRMnI which produced a CH2MnI intermediate via intramolecular aminometallation of CC double bond. Reductive elimination of CH2I from CH2MnI produced iodomethyl heterocycle with the release of Mn(0) which was confirmed by XPS and XRD experiments.

On the understanding of BF3·Et2O-promoted intra- and intermolecular amination and oxygenation of unfunctionalized olefins

Co-reporter:Chun-Hua Yang, Wen-Wen Fan, Gong-Qing Liu, Lili Duan, Lin Li and Yue-Ming Li

RSC Advances 2015 vol. 5(Issue 75) pp:61081-61093

Publication Date(Web):09 Jul 2015

DOI:10.1039/C5RA10513G

BF3·Et2O was found to be effective for both intra- and intermolecular amination and oxygenation of unfunctionalized olefins. In the presence of 3 equiv. of BF3·Et2O, intramolecular hydroamination of N-(pent-4-enyl)-p-toluenesulfonamides, N-(hex-5-enyl)-p-toluenesulfonamides, intermolecular hydroamination between sulfonamides and cyclohexene, norbornene or styrene, lactonization of pent-4-enoic acid or hex-5-enoic acid compounds and esterification of cyclohexene with different carboxylic acids all proceeded readily, leading to the corresponding amination or oxygenation products in up to 99% isolated yields. Preliminary NMR experiments and DFT calculations suggested that the intramolecular hydroamination reactions proceeded via a sulfonimidic acid intermediate (NS–OH), and formation of the corresponding Brønsted acid HF or HBF4 was less likely.

mCPBA-mediated metal-free intramolecular aminohydroxylation and dioxygenation of unfunctionalized olefins

Co-reporter:Gong-Qing Liu, Lin Li, Lili Duan and Yue-Ming Li

RSC Advances 2015 vol. 5(Issue 75) pp:61137-61143

Publication Date(Web):29 Jun 2015

DOI:10.1039/C5RA09024E

mCPBA-mediated metal-free intramolecular aminohydroxylation and dioxygenation reactions of unfunctionalized olefins are reported. In the presence of 1.2 equiv. of m-chlorobenzoic peracid, different N-sulfonyl 4-penten-1-amine substrates could be cyclized via epoxide intermediates, producing the corresponding 2-hydroxymethylpyrrolidine products in up to 92% yields. The reaction could be carried out at gram-scale, and the hydroxyl group could be further converted to a variety of different functional groups via conventional functional group transformation reactions. When N-sulfonyl carboxylimides were subjected to the same reaction, O-cyclization products oxolanimines were obtained. The skeletons of these compounds were confirmed using X-ray diffraction experiments.

Intramolecular Aminoboration of Unfunctionalized Olefins

Co-reporter:Chun-Hua Yang;Yu-Shi Zhang;Wen-Wen Fan;Dr. Gong-Qing Liu;Dr. Yue-Ming Li

Angewandte Chemie International Edition 2015 Volume 54( Issue 43) pp:12636-12639

Publication Date(Web):

DOI:10.1002/anie.201505489

Abstract

A direct and catalyst-free method for the intramolecular aminoboration of unfunctionalized olefins is reported. In the presence of BCl₃ (1 equiv) as the sole boron source, intramolecular aminoboration of sulfonamide derivatives of 4-penten-1-amines, 5-hexen-1-amines, and 2-allylanilines proceeded readily without the use of any catalyst. The boronic acids obtained after hydrolysis could be converted into the corresponding pinacol borates in a straightforward manner by treatment with pinacol under anhydrous conditions.

Modular Preparation of 5-Halomethyl-2-oxazolines via PhI(OAc)2-Promoted Intramolecular Halooxygenation of N-Allylcarboxamides

Co-reporter:Gong-Qing Liu, Chun-Hua Yang, and Yue-Ming Li

The Journal of Organic Chemistry 2015 Volume 80(Issue 22) pp:11339-11350

Publication Date(Web):October 26, 2015

DOI:10.1021/acs.joc.5b01832

A new method for the construction of oxazoline moiety was detailed. Using (diacetoxyiodo)benzene (PIDA) as the reaction promoter and halotrimethylsilane as the halogen source, intramolecular halooxygenation and halothionation of N-allylcarboxamides/N-allylcarbothioamides proceeded readily, leading to the corresponding 5-halomethyloxazolines/5-halomethylthiazolines in good to excellent isolated yields. The 5-halomethyl products could be converted to different derivatives via conventional nucleophilic substitution methods. The reactions were carried out using easily available starting materials, and did not need harsh reaction conditions. All these features made this reaction a viable method for the construction of different oxazoline and thiazoline structures.

Intramolecular Aminoboration of Unfunctionalized Olefins

Co-reporter:Chun-Hua Yang;Yu-Shi Zhang;Wen-Wen Fan;Dr. Gong-Qing Liu;Dr. Yue-Ming Li

Angewandte Chemie 2015 Volume 127( Issue 43) pp:12827-12830

Publication Date(Web):

DOI:10.1002/ange.201505489

Abstract

N,N-Dialkylaniline-assisted thionation of carboxylic amides and esters

Co-reporter:Chun-Hua Yang, Guo-Jing Li, Chao-Jun Gong, Yue-Ming Li

Tetrahedron 2015 Volume 71(Issue 4) pp:637-642

Publication Date(Web):28 January 2015

DOI:10.1016/j.tet.2014.12.030

A new method for thionation of amides and esters was reported. In the presence of catalytic amount of N,N-dialkylanilines, different amides and esters were thionated with good isolated yields under mild conditions using P4S10 as the thionating agent. The reactions were easy to carry out, and the method was effective for both aromatic and aliphatic amides and esters.

The effect of hydrogen bond on Brønsted acid-catalyzed intramolecular hydroamination of unfunctionalized olefins

Co-reporter:Ting-Ting Li, Gong-Qing Liu, Yu-Mei Wang, Bin Cui, Hui Sun, Yue-Ming Li

Tetrahedron 2015 Volume 71(Issue 38) pp:7003-7009

Publication Date(Web):23 September 2015

DOI:10.1016/j.tet.2015.07.003

The catalytic activity of benzoic acid could be increased by introducing a hydrogen bond donor group at the ortho-position. Preliminary DFT calculation indicated that the activation of CC double bond was realized by the action of both the carboxyl group and the hydrogen bond donor. The amino group was brought to the activated CC bond by the interaction between the carboxyl oxygen and amino proton. This interaction also increased the nucleophilicity of the amino group. Thus, in the presence of 20 mol % of 2-(trifluoromethanesulfonamido)benzoic acid, intramolecular hydroamination of unfunctionalized olefins gave the corresponding products in up to 95% isolated yields.

Regioselective Copper(II)-Mediated Bromoamination of Unfunctionalized Olefins: An Efficient Route to N-Heterocyclic Compounds

Co-reporter:Gong-Qing Liu;Zhen-Ying Ding;Li Zhang;Ting-Ting Li;Lin Li;Lili Duan

Advanced Synthesis & Catalysis 2014 Volume 356( Issue 10) pp:2303-2310

Publication Date(Web):

DOI:10.1002/adsc.201301125

Transition metal-free iodine-promoted haloamination of unfunctionalized olefins

Co-reporter:Wei Li, Gong-Qing Liu, Bin Cui, Li Zhang, Ting-Ting Li, Lin Li, Lili Duan and Yue-Ming Li

RSC Advances 2014 vol. 4(Issue 26) pp:13509-13513

Publication Date(Web):04 Mar 2014

DOI:10.1039/C4RA00383G

A transition metal-free route to 3-halopiperidines and 2-halomethylpiperidines was described. In the presence of iodine, potassium persulfate and a suitable halogen source, intramolecular haloamination of 4-penten-1-amines and 5-hexen-1-amines proceeded readily, leading to the corresponding substituted piperidines in good isolated yields.

Cooperative effect in organocatalytic intramolecular hydroamination of unfunctionalized olefins

Co-reporter:Yu-Mei Wang, Ting-Ting Li, Gong-Qing Liu, Li Zhang, Lili Duan, Lin Li and Yue-Ming Li

RSC Advances 2014 vol. 4(Issue 19) pp:9517-9521

Publication Date(Web):23 Jan 2014

DOI:10.1039/C3RA47060A

The cooperative effect in organocatalytic hydroamination of unfunctionalized olefins was reported. In the presence of 3-hydroxy-2-naphthoic acid, N-benzyl 4-penten-1-amines and 5-hexen-1-amines produced the intramolecular cyclization products in good isolated yields.

Trifluoroacetic acid-promoted intramolecular hydroamination of unfunctionalized olefins bearing electron-rich amino groups

Co-reporter:Gong-Qing Liu, Bin Cui, Hui Sun, Yue-Ming Li

Tetrahedron 2014 70(35) pp: 5696-5703

Publication Date(Web):

DOI:10.1016/j.tet.2014.06.061

Regioselective (Diacetoxyiodo)benzene-Promoted Halocyclization of Unfunctionalized Olefins

Co-reporter:Gong-Qing Liu and Yue-Ming Li

The Journal of Organic Chemistry 2014 Volume 79(Issue 21) pp:10094-10109

Publication Date(Web):October 13, 2014

DOI:10.1021/jo501739j

A metal-free method for intramolecular halocyclization of unfunctionalized olefins was detailed. (Diacetoxyiodo)benzene (PIDA) was very effective for haloamidation, haloetherification, and halolactonization of unfunctionalized olefins. In the presence of 1.1 equiv of PIDA and suitable halogen sources, a variety of unfunctionalized olefins could be converted to the corresponding 1,2-bifunctional cyclic skeletons in good to excellent isolated yields, and key intermediates for biologically interesting compounds could be obtained in high yields under mild conditions via nucleophilic substitution of the thus obtained halocyclization products.

A New Method for Intramolecular Chloroamination of Unfunctionalized Olefins

Co-reporter:Gong-Qing Liu;Wei Li

Advanced Synthesis & Catalysis 2013 Volume 355( Issue 2-3) pp:395-402

Publication Date(Web):

DOI:10.1002/adsc.201200352

Abstract

A new method for the intramolecular chloroamination of unfunctionalized olefins is reported. The reactions were carried out at room temperature for 3 h using hydrated copper(II) chloride as both promoter and chlorine source, and the corresponding vincinal haloamines were obtained in good isolated yields.

One-pot preparation of 3-chloropiperidine compounds via Cu(II)-promoted intramolecular chloroamination of unfunctionalized olefins

Co-reporter:Run-Lin Li, Gong-Qing Liu, Wei Li, Yu-Mei Wang, Lin Li, Lili Duan, Yue-Ming Li

Tetrahedron 2013 69(29) pp: 5867-5873

Publication Date(Web):

DOI:10.1016/j.tet.2013.05.022

Ligand acceleration in ZnI2-catalyzed intramolecular hydroamination of unfunctionalized olefins

Co-reporter:Gong-Qing Liu, Wei Li, Yu-Mei Wang, Zhen-Ying Ding, Yue-Ming Li

Tetrahedron Letters 2012 Volume 53(Issue 33) pp:4393-4396

Publication Date(Web):15 August 2012

DOI:10.1016/j.tetlet.2012.06.033

Zinc halide-promoted hydroamination of 4-penten-1-amine compounds was studied. Preliminary results indicated that both steric and electronic factors are crucial for this Lewis acid-promoted reaction. ZnI2 gave the most promising results and the reactivity could be further increased upon addition of a suitable ligand. Up to 95% isolated yields were obtained when the reactions were carried out in 1,4-dioxane in the presence of 10 mol % of ZnI2 and 8-hydroxyquinoline.Catalyst = 10 mol % ZnI2 + 10 mol % ligand, yields up to 95%.

Zinc triflate-catalyzed intermolecular hydroamination of vinylarenes and anilines: scopes and limitations

Co-reporter:Gong-Qing Liu, Yue-Ming Li

Tetrahedron Letters 2011 Volume 52(Issue 52) pp:7168-7170

Publication Date(Web):28 December 2011

DOI:10.1016/j.tetlet.2011.10.124

Intermolecular hydroamination of vinylarenes and anilines was studied using zinc triflate as catalyst. NMR experiments supported a Lewis acid activation of the CC double bond. Electronic/steric effect study indicated that Lewis acidity of the catalyst as well as the coordination property of the amine were the governing factors for successful hydroamination of the substrates. More nucleophilic amine would bind more tightly to the central metal, leading to an unproductive coordination. Approach of bulky amine to CC bond would be hindered, and an alternative electrophilic substitution on benzene ring of the amine would become the major reaction. Electrophilic substitution would become predominant when strong electron-donating group is presented on aniline benzene ring.