Co-reporter:Yong Tang
Science Bulletin 2016 Volume 61( Issue 12) pp:914-916
Publication Date(Web):2016 June
DOI:10.1007/s11434-016-1096-9
Co-reporter:Dr. Chuan Liu;Ji-Cheng Yi;Dr. Zhong-Bo Zheng;Dr. Yong Tang; Li-Xin Dai;Dr. Shu-Li You
Angewandte Chemie International Edition 2016 Volume 55( Issue 2) pp:751-754
Publication Date(Web):
DOI:10.1002/anie.201508570
Abstract
A direct asymmetric dearomative amination of tryptamines with O-(2,4-dinitrophenyl)hydroxylamine (DPH) was achieved using CuBr-bisoxazoline complex as a catalyst, affording 3a-amino-pyrroloindolines in good to excellent enantioselectivity under mild reaction conditions. Furthermore, the synthetic value of this method was demonstrated in the total synthesis of (−)-psychotriasine in a highly concise manner.
Co-reporter:Dr. Chuan Liu;Ji-Cheng Yi;Dr. Zhong-Bo Zheng;Dr. Yong Tang; Li-Xin Dai;Dr. Shu-Li You
Angewandte Chemie 2016 Volume 128( Issue 2) pp:761-764
Publication Date(Web):
DOI:10.1002/ange.201508570
Abstract
A direct asymmetric dearomative amination of tryptamines with O-(2,4-dinitrophenyl)hydroxylamine (DPH) was achieved using CuBr-bisoxazoline complex as a catalyst, affording 3a-amino-pyrroloindolines in good to excellent enantioselectivity under mild reaction conditions. Furthermore, the synthetic value of this method was demonstrated in the total synthesis of (−)-psychotriasine in a highly concise manner.
Co-reporter:Pan Wang; Liang-Wen Feng; Lijia Wang; Jun-Fang Li; Saihu Liao
Journal of the American Chemical Society 2015 Volume 137(Issue 14) pp:4626-4629
Publication Date(Web):March 25, 2015
DOI:10.1021/jacs.5b01517
This study has led to the development of a novel, highly efficient, 1,2-perfluoro-alkyl/-aryl migration process in reactions of hydrate of 1-perfluoro-alkyl/-aryl-1,2-diketones with alcohols, which are promoted by a Zn(II)/bisoxazoline and form α-perfluoro-alkyl/-aryl-substituted α-hydroxy esters. With (−)-8-phenylmenthol as the alcohol, the corresponding menthol esters are generated in high yields with excellent levels of diastereoselectivity. The mechanistic studies show that the benzilic ester-type rearrangement reaction takes place via an unusual 1,2-migration of electron-deficient trifluoromethyl group rather than the phenyl group. The overall process serves as a novel, efficient, and simple approach for the synthesis of highly enantioenriched, biologically relevant α-hydroxy-α-perfluoroalkyl carboxylic acid derivatives.
Co-reporter:Hao Xu; Jiang-Lin Hu; Lijia Wang; Saihu Liao
Journal of the American Chemical Society 2015 Volume 137(Issue 25) pp:8006-8009
Publication Date(Web):June 12, 2015
DOI:10.1021/jacs.5b04429
An efficient [4 + 3] cycloaddition reaction of D–A cyclopropanes with dienes has been successfully developed. The reaction proceeds well with various dienolsilyl ethers in the presence of Lewis acid, delivering a variety of cycloheptenes and [n,5,0]carbobicycles with excellent stereoselectivity. The asymmetric version of this reaction is also realized using a newly designed chiral Cy-TOX ligand, providing a new approach to access optically active cycloheptenes and [n,5,0]carbobicycles. Mechanisic study reveals that the reaction involves a stepwise pathway, which undergoes an unusual ring opening of five-membered [3 + 2] intermediate and sequential intramolecular cyclization to afford the thermodynamically stable [4 + 3] annulation product.
Co-reporter:Hai Ren, Pan Wang, Lijia Wang, and Yong Tang
Organic Letters 2015 Volume 17(Issue 19) pp:4886-4889
Publication Date(Web):September 24, 2015
DOI:10.1021/acs.orglett.5b02440
A highly enantioselective and regioselective chiral Lewis acid catalyzed tandem Friedel–Crafts/lactonization reaction is reported, providing direct access to plenty of 3-hydroxy-3-trifluoromethyl benzofuran-2-ones in up to 94% yields with up to >99% ee. Mechanistic study reveals that the interactions between the phenolic hydroxyl group and trifluoropyruvate are the most likely contributing factor to the high enantio- and regioselectivity. Optically pure (−)-BHFF can be obtained in gram-scale with 0.05 mol % catalyst, demonstrating the potentially utility of this method in medicinal chemistry.
Co-reporter:Xiaoguang Zhou, Bing Wei, Xiu-Li Sun, Yong Tang and Zuowei Xie
Chemical Communications 2015 vol. 51(Issue 26) pp:5751-5753
Publication Date(Web):19 Feb 2015
DOI:10.1039/C4CC10032H
A new class of chiral zirconium complexes supported by chiral tridentate [O−NO−]-type of ligands derived from amino acids were synthesized and structurally characterized. They catalyzed asymmetric hydroamination/cyclization of primary aminoalkenes to give five- and six-membered N-heterocyclic amines with up to 94% ee.
Co-reporter:Liang-Wen Feng;Peng Wang;Lijia Wang
Science Bulletin 2015 Volume 60( Issue 2) pp:210-215
Publication Date(Web):2015 January
DOI:10.1007/s11434-014-0708-5
A copper-catalyzed highly stereoselective cyclopropanation of 1,2-disubstituted olefins with α-nitrodiazo acetates has been developed, giving the desired products in up to 97 % yields, up to >99/1 dr and up to 98 % ee, which provides an efficient access to the synthesis of optical active cyclopropane α-amino acids and unnatural α-amino acid derivatives.
Co-reporter:Saihu Liao, Xiu-Li Sun, and Yong Tang
Accounts of Chemical Research 2014 Volume 47(Issue 8) pp:2260-2272
Publication Date(Web):May 16, 2014
DOI:10.1021/ar800104y
This Account describes our efforts toward this goal. Based on this side arm strategy, we have developed two series of ligands based on the bisoxazoline framework; namely, trisoxazoline (TOX) ligands and side armed bisoxazoline (SaBOX). The “side arms” are shown to play multiple roles in different cases, for example, as a ligating group, a steric group, or a directing group, which are dependent on the metal and the functionality at the side arm. Metal catalysts based on these ligands have proven to be highly efficient for a number of asymmetric transformations, including Friedel–Crafts reaction, Kinugasa reaction, Nazarov reaction, 1,2-Stevens rearrangement, Cannizzaro reaction, and cyclopropanation. In comparison with the parent BOX ligands, the metal catalysts based on these TOX and SaBOX ligands usually exhibit higher efficiency and diastereo- and enantioselectivity with better impurity tolerance and stability. Moreover, in several TOX–metal complex catalyzed reactions such as Friedel–Crafts reaction and [3 + 2] cycloaddition, stereoselectivity could be switched based on reaction conditions. These ligands were particularly prominent in the remote controls of enantioselection such as the conjugate additions to alkylidene malonates and ring-opening/cyclization cascades of cyclopropanes, for which high stereoselectivity is usually difficult to achieve due to the poor chiral communication. The works by us and other groups have demonstrated that the side arm strategy can be employed as a general principle for ligand and catalyst design and should not be limited to the BOX scaffolds and the reactions described in this Account. Wide application of the new strategy in organometallic homogeneous catalysis can be anticipated.
Co-reporter:Peng Wang, Saihu Liao, Jian-Bo Zhu and Yong Tang
Chemical Communications 2014 vol. 50(Issue 7) pp:808-810
Publication Date(Web):06 Nov 2013
DOI:10.1039/C3CC45286G
A new ylide-initiated tandem cyclization reaction based on γ-dialkylation of allylic ylides has been realized, delivering a series of [3.3.0] oxa-bicyclic dienes in high yields with perfect diastereoselectivity.
Co-reporter:Qikai Kang;Lijia Wang;Zhongbo Zheng;Junfang Li
Chinese Journal of Chemistry 2014 Volume 32( Issue 8) pp:669-672
Publication Date(Web):
DOI:10.1002/cjoc.201400053
Abstract
A new type of trisoxazoline and bisthiazoline based ligands have been developed,which are absent of chiral motif on the parent skeleton and containa chiral backbone on sidearm. The ligands promote the amine nucleophilic ring opening reaction of 1,1-cyclopropane diesters smoothly, furnishing the γ-amino acid derivatives in high yield with moderate to good enantioselectivity.
Co-reporter:Zheng Wang;Ai-Qing Peng;Xiu-Li Sun
Science China Chemistry 2014 Volume 57( Issue 8) pp:1144-1149
Publication Date(Web):2014 August
DOI:10.1007/s11426-014-5137-4
Titanium complexes derived from 2,4-di-tert-butyl-6-((2-(arylsulfinyl)phenylimino)methyl)phenol are designed and synthesized. X-ray diffraction studies reveal that the complexes adopt distorted octahedral geometry with O(phenol), N(imine), and O(sulfoxide) coordinated with titanium. Combined with modified methylaluminoxane(MMAO), the complexes exhibit moderate to high activity to afford polyethylene even at 120 °C under 1 atm ethylene pressure. The complexes also show excellent capability in copolymerization of ethylene with either 1-hexene or norbornene. Results indicate that the introduction of sulfoxide groups could open the space around central metal and favors the insertion of bulky comonomers.
Co-reporter:Pan Wang ; Wen-Jie Tao ; Xiu-Li Sun ; Saihu Liao
Journal of the American Chemical Society 2013 Volume 135(Issue 45) pp:16849-16852
Publication Date(Web):October 25, 2013
DOI:10.1021/ja409859x
An asymmetric intramolecular Cannizzaro reaction of aryl and alkyl glyoxals with alcohols has been realized with an unprecedented high level of enantioselectivity, on the basis of a newly developed congested TOX ligand and a gradual liberation protocol of active glyoxals from glyoxal monohydrates. Preliminary results suggested a mechanism of enantioselective addition of alcohols to glyoxals contributing most to the stereoselectivity, other than by the dynamic kinetic resolution of hemiacetal intermediates.
Co-reporter:Peng Wang, Saihu Liao, Jian-Bo Zhu, and Yong Tang
Organic Letters 2013 Volume 15(Issue 14) pp:3606-3609
Publication Date(Web):July 5, 2013
DOI:10.1021/ol4014552
An unexpected three-component iron-catalyzed reaction, comprising C–C bond cleavages in two components together with three times the cyclopropane formation and ring opening, is developed. The current reaction provides an unprecedented and efficient approach for the synthesis of cyclopentadienes in high yields.
Co-reporter:Jian-Bo Zhu, Peng Wang, Saihu Liao and Yong Tang
Chemical Communications 2013 vol. 49(Issue 40) pp:4570-4572
Publication Date(Web):28 Mar 2013
DOI:10.1039/C3CC41435C
With the mediation of phosphine, the direct intramolecular coupling of two electrophiles – alkyl halides with electron-deficient olefins – has been successfully realized in an intramolecular conjugate addition manner. The reaction provides a new approach for the synthesis of chromans and relevant analogues.
Co-reporter:Peng Wang, Saihu Liao, Sunewang R. Wang, Run-Duo Gao and Yong Tang
Chemical Communications 2013 vol. 49(Issue 67) pp:7436-7438
Publication Date(Web):24 Jun 2013
DOI:10.1039/C3CC44092C
The unprecedented reaction of trisubstituted alkenes with iron porphyrin carbenes has been successfully developed. Both multiply substituted 1,3-butadiene and cyclopentadiene products are readily accessible with high efficiency and selectivity in good yields.
Co-reporter:Zhou Chen, Jun-Fang Li, Wen-Jie Tao, Xiu-Li Sun, Xiao-Hong Yang, and Yong Tang
Macromolecules 2013 Volume 46(Issue 7) pp:2870-2875
Publication Date(Web):March 27, 2013
DOI:10.1021/ma400283p
A series of titanium complexes bearing [ONX] tridentate ligands have been synthesized and characterized. The complexes containing sulfur or phosphine donors showed high activity in the copolymerization of ethylene with 9-decen-1-ol (up to 1.3 × 108 g polymer (mol Ti)−1 h–1) with an incorporation ratio of up to 8.8 mol %. Moreover, they have also shown excellent capability for copolymerization of ethylene with AlBui3 (or tert-butylchlorodimethylsilane) pretreated 4-penten-1-ol, ω-alkenoic acid, and ω-alkenoic ester, as well as unprotected tertiary amine.
Co-reporter:You-Yun Zhou;Jun Li;Lin Ling;Dr. Sai-Hu Liao;Dr. Xiu-Li Sun;Dr. Yu-Xue Li;Dr. Li-Jia Wang ;Dr. Yong Tang
Angewandte Chemie International Edition 2013 Volume 52( Issue 5) pp:1452-1456
Publication Date(Web):
DOI:10.1002/anie.201207576
Co-reporter:Peng Wang;Dr. Lin Ling;Dr. Sai-Hu Liao;Jian-Bo Zhu;Sunewang R. Wang;Dr. Yu-Xue Li;Dr. Yong Tang
Chemistry - A European Journal 2013 Volume 19( Issue 21) pp:6766-6773
Publication Date(Web):
DOI:10.1002/chem.201204182
Abstract
An Umpolung approach, in which a phosphorus ylide moiety was introduced to increase the electron density of the double bond, was developed to activate electron-deficient alkenes for reaction with electrophilic iron carbenes. In tandem with the Wittig reaction, the reactions of α,β-unsaturated esters with in situ generated Fecarbene complexes delivered formal CH insertion products through cyclopropanation/ring-opening reactions. DFT calculations and cross-experiments indicate that, in this process, the ring opening of the cyclopropylmethyl ylide intermediate is rapid and reversible and the subsequent proton transfer is the rate-determining step. Further studies revealed that, based on the choice of the ylide and ester groups, as well as the base, the reaction could be steered towards either the ring-opening pathway or to the production of vinyl cyclopropanes.
Co-reporter:Zhen-Cao Shu, Jian-Bo Zhu, Saihu Liao, Xiu-Li Sun, Yong Tang
Tetrahedron 2013 69(1) pp: 284-292
Publication Date(Web):
DOI:10.1016/j.tet.2012.10.028
Co-reporter:Wen-Jie Tao;Dr. Jun-Fang Li;Ai-Qing Peng;Dr. Xiu-Li Sun;Xiao-Hong Yang ;Dr. Yong Tang
Chemistry - A European Journal 2013 Volume 19( Issue 41) pp:13956-13961
Publication Date(Web):
DOI:10.1002/chem.201300890
Abstract
By a reasonable combination of the Wacker reaction and olefin polymerization processes, water proves to be an excellent activator for the palladium(II)-catalyzed polymerization of ethylene and it provides a safe, environmental-friendly and handy initiator for olefin polymerization. The activity of the olefin polymerization is comparable to reactions catalyzed by the corresponding alkylated cationic palladium complexes.
Co-reporter:Carl Redshaw and Yong Tang
Chemical Society Reviews 2012 vol. 41(Issue 12) pp:4484-4510
Publication Date(Web):16 May 2012
DOI:10.1039/C2CS35028A
The opening up of new markets, particularly in the Far East, is expected to increase the industrial demand for more (and new) plastic materials. In turn, this will drive the need for further catalyst development, with increased efficiency and with the capacity to easily control the resulting polymer properties being high on the agenda. With this in mind, tailoring the pre-catalyst structure has proved to be a very successful strategy, and has allowed for the elucidation of a number of structure–activity trends. A particularly fruitful synthetic avenue has been the deployment of multi-dentate ancillary ligands bearing one or more substituents containing additional functionality, capable of weakly binding to the metal. Such a method is versatile and allows for the incorporation of a wide range of functionality. Furthermore, benefits of such an approach include the ability to control the % incorporation of co-monomers, in situ screening, low co-catalyst loadings (versus activity enhancement) as well as control over the resultant polymer structure. This review underlines the efforts made in the last few years with regard to the use of tridentate ligands and beyond in the field of α-olefin polymerization using catalytic systems based on group IV metals.
Co-reporter:Peng Wang, Chun-Rong Liu, Xiu-Li Sun, Shuai-Shuai Chen, Jun-Fang Li, Zuowei Xie and Yong Tang
Chemical Communications 2012 vol. 48(Issue 2) pp:290-292
Publication Date(Web):08 Nov 2011
DOI:10.1039/C1CC16747B
A newly designed PE-supported arsine has been developed as an excellent catalyst for catalytic Wittig-type olefination. Simple ketones, in particular inactive ketones prove to be suitable substrates for the first time. This reaction provides an easy access to di-, tri-, and tetra-substituted olefins in high yield.
Co-reporter:Rui Zhou;Xianming Deng;Juncheng Zheng;Qi Sheng;Xiuli Sun
Chinese Journal of Chemistry 2011 Volume 29( Issue 5) pp:995-1000
Publication Date(Web):
DOI:10.1002/cjoc.201190202
Abstract
1-Aminocyclopropanecarboxylic acid derivatives are synthesized from readily available dehydroamino acid derivatives via sulfur ylide. A range of different ylides are employed and the corresponding aminocyclopropanes are afforded with reasonable diastereoselection in good yields.
Co-reporter:Yong Tang
Science Bulletin (June 2016) Volume 61(Issue 12) pp:914-916
Publication Date(Web):1 June 2016
DOI:10.1007/s11434-016-1096-9
Co-reporter:Xiaoguang Zhou, Bing Wei, Xiu-Li Sun, Yong Tang and Zuowei Xie
Chemical Communications 2015 - vol. 51(Issue 26) pp:NaN5753-5753
Publication Date(Web):2015/02/19
DOI:10.1039/C4CC10032H
A new class of chiral zirconium complexes supported by chiral tridentate [O−NO−]-type of ligands derived from amino acids were synthesized and structurally characterized. They catalyzed asymmetric hydroamination/cyclization of primary aminoalkenes to give five- and six-membered N-heterocyclic amines with up to 94% ee.
Co-reporter:Jian-Bo Zhu, Peng Wang, Saihu Liao and Yong Tang
Chemical Communications 2013 - vol. 49(Issue 40) pp:NaN4572-4572
Publication Date(Web):2013/03/28
DOI:10.1039/C3CC41435C
With the mediation of phosphine, the direct intramolecular coupling of two electrophiles – alkyl halides with electron-deficient olefins – has been successfully realized in an intramolecular conjugate addition manner. The reaction provides a new approach for the synthesis of chromans and relevant analogues.
Co-reporter:Peng Wang, Saihu Liao, Jian-Bo Zhu and Yong Tang
Chemical Communications 2014 - vol. 50(Issue 7) pp:NaN810-810
Publication Date(Web):2013/11/06
DOI:10.1039/C3CC45286G
A new ylide-initiated tandem cyclization reaction based on γ-dialkylation of allylic ylides has been realized, delivering a series of [3.3.0] oxa-bicyclic dienes in high yields with perfect diastereoselectivity.
Co-reporter:Peng Wang, Saihu Liao, Sunewang R. Wang, Run-Duo Gao and Yong Tang
Chemical Communications 2013 - vol. 49(Issue 67) pp:NaN7438-7438
Publication Date(Web):2013/06/24
DOI:10.1039/C3CC44092C
The unprecedented reaction of trisubstituted alkenes with iron porphyrin carbenes has been successfully developed. Both multiply substituted 1,3-butadiene and cyclopentadiene products are readily accessible with high efficiency and selectivity in good yields.
Co-reporter:Peng Wang, Chun-Rong Liu, Xiu-Li Sun, Shuai-Shuai Chen, Jun-Fang Li, Zuowei Xie and Yong Tang
Chemical Communications 2012 - vol. 48(Issue 2) pp:NaN292-292
Publication Date(Web):2011/11/08
DOI:10.1039/C1CC16747B
A newly designed PE-supported arsine has been developed as an excellent catalyst for catalytic Wittig-type olefination. Simple ketones, in particular inactive ketones prove to be suitable substrates for the first time. This reaction provides an easy access to di-, tri-, and tetra-substituted olefins in high yield.
Co-reporter:Carl Redshaw and Yong Tang
Chemical Society Reviews 2012 - vol. 41(Issue 12) pp:NaN4510-4510
Publication Date(Web):2012/05/16
DOI:10.1039/C2CS35028A
The opening up of new markets, particularly in the Far East, is expected to increase the industrial demand for more (and new) plastic materials. In turn, this will drive the need for further catalyst development, with increased efficiency and with the capacity to easily control the resulting polymer properties being high on the agenda. With this in mind, tailoring the pre-catalyst structure has proved to be a very successful strategy, and has allowed for the elucidation of a number of structure–activity trends. A particularly fruitful synthetic avenue has been the deployment of multi-dentate ancillary ligands bearing one or more substituents containing additional functionality, capable of weakly binding to the metal. Such a method is versatile and allows for the incorporation of a wide range of functionality. Furthermore, benefits of such an approach include the ability to control the % incorporation of co-monomers, in situ screening, low co-catalyst loadings (versus activity enhancement) as well as control over the resultant polymer structure. This review underlines the efforts made in the last few years with regard to the use of tridentate ligands and beyond in the field of α-olefin polymerization using catalytic systems based on group IV metals.