Co-reporter:Zhiyong Hu, Xiaofeng Tong, and Guixia Liu
Organic Letters 2016 Volume 18(Issue 9) pp:2058-2061
Publication Date(Web):April 13, 2016
DOI:10.1021/acs.orglett.6b00689
A rhodium(III)-catalyzed cascade cyclization/electrophilic amidation using N-pivaloyloxylamides as the electrophilic nitrogen source has been developed. This protocol provides an efficient route for the synthesis of 3-amidoindoles and 3-amidofurans under mild conditions with good functional group tolerance. The synthetic utility of this reaction has been demonstrated through the derivatization of the 3-amidoindoles to several heterocycle-fused indoles.
Co-reporter:Yiting Gu; Pengfei Hu; Chunjie Ni
Journal of the American Chemical Society 2015 Volume 137(Issue 19) pp:6400-6406
Publication Date(Web):April 23, 2015
DOI:10.1021/jacs.5b03273
Two classes of phosphine-catalyzed addition/cycloaddition domino reactions of β′-acetoxy allenoate 1 have been developed. The reaction of 1 with 2-acyl-3-methyl-acrylonitrile 2 readily occurs to give 2-oxabicyclo[3.3.1]nonane 3, furnishing the β′-addition/[4 + 4] cycloaddition domino sequence. In this sequence, β′C of allenoate 1 is an electrophilic center, and its β′C and γC serve as a 1,4-dipole. When the other reaction partner is switched to 2-acyl-3-(2-pyrrole)-acrylonitrile 8, a γ-addition/[3 + 2] cycloaddition domino reaction is instead observed, in which allenoate 1 exhibits dual electrophilic reactivity of γC and 1,3-dipole chemical behavior of βC and β′C. Furthermore, both of these two asymmetric variants have also been achieved with up to 93% ee. The domino reactions presented in this report are valuable for highly stereoselective construction of complex structures under mild reaction conditions.
Co-reporter:Falin Li, Jiangfei Chen, Yading Hou, Yujie Li, Xin-Yan Wu, and Xiaofeng Tong
Organic Letters 2015 Volume 17(Issue 21) pp:5376-5379
Publication Date(Web):October 15, 2015
DOI:10.1021/acs.orglett.5b02724
The thermal 1,3-dipolar cycloadditions of 4-acetoxyallenoates 1 with various dipoles have been reported. When azomethine imines and nitrones are used as the 1,3-dipole partner, the corresponding reactions afford 2,3-dihydropyrazole and 2,3-dihydroisoxazole derivatives, respectively. These reactions might proceed via a thermal 1,3-dipolar cycloaddition and the subsequent elimination of HOAc. In addition, allenoates 1 react well with in situ generated azomethine ylides in which a similar cycloaddition pathway is followed by oxidative aromatization to give indolizine derivatives.
Co-reporter:Yiting Gu, Falin Li, Pengfei Hu, Daohua Liao, and Xiaofeng Tong
Organic Letters 2015 Volume 17(Issue 5) pp:1106-1109
Publication Date(Web):February 18, 2015
DOI:10.1021/acs.orglett.5b00359
The DABCO-catalyzed divergent (4 + 2) annulations of δ-acetoxy allenoates 1 are reported. The chemical behavior of 1 under DABCO catalyst was found to be substrate dependent. Allenoate 1 with an aromatic group at δC preferentially reacted with salicylaldehyde derivative 2, delivering 4H-chromenes 3. On the other hand, allenoates 1 with an alkyl group at δC readily underwent (4 + 2) annulations with oxo diene 4 to afford 4H-pyrans 5.
Co-reporter:Shasha Quan, Yuanyuan Wang, Kewen Zheng, Xiaofeng Tong
Tetrahedron Letters 2015 Volume 56(Issue 1) pp:215-217
Publication Date(Web):1 January 2015
DOI:10.1016/j.tetlet.2014.11.063
Hydrative cyclization of 1,6-allenyne catalyzed by simple RhCl3 in aqueous solvent is described. This reaction proceeds in rarely reported fashion of 6-endo cyclization and provides a facile access to 5,6-dihydropyrans and 3,4-dehydropiperidines from acyclic substrates in moderate to good yields.
Co-reporter:Mian Cheng, Jian-Kang Liu, Xiaofeng Tong, Ping Tian
Tetrahedron Letters 2015 Volume 56(Issue 25) pp:3864-3867
Publication Date(Web):17 June 2015
DOI:10.1016/j.tetlet.2015.04.099
A chiral secondary amine-promoted asymmetric [4+2] cycloadditions of α-acetoxymethyl allenoate 1 and electron-deficient alkenes 2 have been developed. The reaction features the utilization of addition–elimination reaction between allenoate 1 and the secondary amine to generate the key 2-aminobutadiene intermediate, which subsequently undergoes [4+2] cycloaddition with alkenes in a stepwise fashion, delivering the substituted cyclohexenes with good stereoselectivity.
Co-reporter:Qiang Liu, Chen Chen, Xiaofeng Tong
Tetrahedron Letters 2015 Volume 56(Issue 30) pp:4483-4485
Publication Date(Web):22 July 2015
DOI:10.1016/j.tetlet.2015.05.094
A catalysis system comprised of Pd(cod)Cl2 precursor and IMes ligand has been developed, which is efficient to catalyze the atom transfer radical cyclization of N-allyl-α-chloroamides with the help of NaI additive. This reaction provides a facile access to β-iodomethyl-γ-lactam with high stereoselectivity. Moreover, the results from the reaction of deuterium-labeled substrate and TEMPO-trapping experiment clearly indicate that radical intermediate(s) should be involved in the reaction.
Co-reporter:Chen Chen;Longlei Hou;Mian Cheng; Jianhua Su ;Dr. Xiaofeng Tong
Angewandte Chemie 2015 Volume 127( Issue 10) pp:3135-3139
Publication Date(Web):
DOI:10.1002/ange.201410996
Abstract
Although the advances on carbon halide reductive elimination have been made, the alkyl bromide and chloride analogues remain a challenge. Here, a palladium(0)-catalyzed iminohalogenation of γ,δ-unsaturated oxime esters is described, and the use of electron-poor phosphine ligands proved to be crucial to promoting alkyl bromide and chloride reductive elimination. Furthermore, SN2-type alkyl bromide and chloride reductive elimination has also been established.
Co-reporter:Chen Chen;Longlei Hou;Mian Cheng; Jianhua Su ;Dr. Xiaofeng Tong
Angewandte Chemie International Edition 2015 Volume 54( Issue 10) pp:3092-3096
Publication Date(Web):
DOI:10.1002/anie.201410996
Abstract
Although the advances on carbon halide reductive elimination have been made, the alkyl bromide and chloride analogues remain a challenge. Here, a palladium(0)-catalyzed iminohalogenation of γ,δ-unsaturated oxime esters is described, and the use of electron-poor phosphine ligands proved to be crucial to promoting alkyl bromide and chloride reductive elimination. Furthermore, SN2-type alkyl bromide and chloride reductive elimination has also been established.
Co-reporter:Wei Dong, Pengfei Hu, Jian Hu, Xiaofeng Tong
Tetrahedron Letters 2014 Volume 55(Issue 10) pp:1682-1685
Publication Date(Web):5 March 2014
DOI:10.1016/j.tetlet.2013.10.059
A divergent isomerization of 5-hydroxyl-2,3-dienoate 1 catalyzed by Lewis base has been developed, the phosphine catalyst leads to 5-oxohex-2(3)-enoates 2 while DABCO catalyst affords 3-ethoxy α,β-unsaturated lactone 3.
Co-reporter:Zheng Xie, Pan Wu, Liangzhen Cai, Xiaofeng Tong
Tetrahedron Letters 2014 Volume 55(Issue 13) pp:2160-2162
Publication Date(Web):26 March 2014
DOI:10.1016/j.tetlet.2014.02.087
This Letter describes a palladium-catalyzed cyclization of vinyl iodide-tethered allensulfonamide in the presence of alkylol, which provides a facile access to 2-alkoxy-3-methylene-tetrahydropyridine. The asymmetric version of this reaction has also been preliminarily realized with up to 81% enantioselectivity when chiral bisphosphine ligands were used.
Co-reporter:Chen Chen, Jian Hu, Jianhua Su, Xiaofeng Tong
Tetrahedron Letters 2014 Volume 55(Issue 21) pp:3229-3231
Publication Date(Web):21 May 2014
DOI:10.1016/j.tetlet.2014.04.019
Pd(0)-catalyzed carboiodonation of but-3-enylcarbamic chloride has been developed with NaI as additive, which provides a ready access to substituted γ-lactam bearing an alkyl iodide group. This reaction features alkyl iodide reductive elimination as a key step in catalytic cycle, indicating the crucial role of additive NaI.
Co-reporter:Chen Chen; Jianhua Su ;Dr. Xiaofeng Tong
Chemistry - A European Journal 2013 Volume 19( Issue 16) pp:5014-5018
Publication Date(Web):
DOI:10.1002/chem.201204039
Co-reporter:Pengfei Hu;Jian Hu; Jiajun Jiao ;Dr. Xiaofeng Tong
Angewandte Chemie 2013 Volume 125( Issue 20) pp:5427-5430
Publication Date(Web):
DOI:10.1002/ange.201300526
Co-reporter:Pengfei Hu;Jian Hu; Jiajun Jiao ;Dr. Xiaofeng Tong
Angewandte Chemie International Edition 2013 Volume 52( Issue 20) pp:5319-5322
Publication Date(Web):
DOI:10.1002/anie.201300526
Co-reporter:Jian Hu, Wei Dong, Xin-Yan Wu, and Xiaofeng Tong
Organic Letters 2012 Volume 14(Issue 21) pp:5530-5533
Publication Date(Web):October 23, 2012
DOI:10.1021/ol302634p
Phosphine-catalyzed (3 + 2) and (3 + 3) annulations between 5-acetoxypenta-2,3-dienoate and 1C,3O-bisnucleophiles are presented. The former cases can be achieved with the assistance of base while the latter is dominant without any additive. A series of deuterium-labeling experiments disclosed that the divergence in annulations is likely determined by the involved proton transfer processes.
Co-reporter:Kun Li, Jian Hu, Hui Liu and Xiaofeng Tong
Chemical Communications 2012 vol. 48(Issue 23) pp:2900-2902
Publication Date(Web):23 Jan 2012
DOI:10.1039/C2CC30242J
A DABCO-catalyzed (3 + 3) annulation between 2-(acetoxymethyl)buta-2,3-dienoate and sulfur ylides has been developed, which provides a facile method for the synthesis of 4H-pyrans bearing a vinyl sulfide group.
Co-reporter:Jian Hu, Bing Tian, Xinyan Wu, and Xiaofeng Tong
Organic Letters 2012 Volume 14(Issue 19) pp:5074-5077
Publication Date(Web):September 20, 2012
DOI:10.1021/ol302329b
In this paper, an amine-triggered cascade SN2/cycloaddtion sequence between 2-(acetoxymethyl)buta-2,3-dienoate 1 and various π-system functionalized tosylamides 3 has been reported, which provides a facile method for stereoselective construction of structurally diverse azaheterocycles.
Co-reporter:Pan Wu, Hui Liu, Xiaofeng Tong
Tetrahedron Letters 2012 Volume 53(Issue 35) pp:4673-4675
Publication Date(Web):29 August 2012
DOI:10.1016/j.tetlet.2012.06.075
This Letter describes the Pd(0)-catalyzed domino Heck–aza-Michael reaction between (Z)-N-(3-iodoallyl)-tosylamide and acrylic ester. The reaction provides a facile access to an important class of substituted 3-pyrroline.
Co-reporter:Hui Liu ; Chaolong Li ; Dong Qiu
Journal of the American Chemical Society 2011 Volume 133(Issue 16) pp:6187-6193
Publication Date(Web):April 1, 2011
DOI:10.1021/ja201204g
A palladium-catalyzed iodine atom transfer cycloisomerization of (Z)-1-iodo-1,6-diene has been developed, which provides a facile method to construct six-memebered heterocycles bearing an alkyl iodide group. The ligand screening shows that both the type and the quantity of ligand impose significant influences on this transformation, and the combination of 30 mol % 1,1′-bis(diphenylphosphino)ferrocene (DPPF) and 10 mol % Pd(OAc)2 is the optimal choice. The catalytic cycle, consisting of oxidative addition of Pd(0) to vinyl iodide, intramolecular alkene insertion, and alkyl iodide reductive elimination, has been proposed and eventually supported by convincing evidence from a series of control experiments. More importantly, these control experiments disclose some features of the event of alkyl iodide reductive elimination: (1) this reductive elimination is proved to be a stereospecific process; and (2) both alkyl iodide oxidative addition and reductive elimination are not effected by a TEMPO additive. Besides its ability to undergo oxidative addition, the catalyst (palladium + DPPF) could also promote a radical transfer process. The findings described in this paper will be helpful for further development of the metal-catalyzed formation of a carbon−halide bond.
Co-reporter:Jian Hu, Yabing Wei, and Xiaofeng Tong
Organic Letters 2011 Volume 13(Issue 12) pp:3068-3071
Publication Date(Web):May 16, 2011
DOI:10.1021/ol200940a
In this paper, a reagent-controlled [3 + 2] annulation of γ-functionalized butynoates 1 and 1C,3O-bisnucleophiles 2 is reported, which leads to three distinct furan skeletons 3–5. A PPh3 catalyst preferentially attached the β-position of 1a, facilitating α-addition to furnish Type I annulations. With the assistance of Ag2O, Type II annulations were achieved via selective γ-substitution. In the absence of the PPh3 catalyst, the reagent Cs2CO3 promoted β-addition to realize Type III annulations.
Co-reporter:Hui Liu, Chen Chen, Limin Wang, and Xiaofeng Tong
Organic Letters 2011 Volume 13(Issue 19) pp:5072-5075
Publication Date(Web):September 12, 2011
DOI:10.1021/ol2022388
A palladium-catalyzed iodoalkynation of norbornene has been realized with the use of alkynyl iodides 1, which is found to be strongly solvent-dependent. MeCN favors 1,7-iodoalkylation product 3 while CCl4 leads to 1,2-iodoalkylation product 4.
Co-reporter:Hui Liu, Limin Wang and Xiaofeng Tong
Chemical Communications 2011 vol. 47(Issue 44) pp:12206-12208
Publication Date(Web):03 Oct 2011
DOI:10.1039/C1CC15257B
A Pd(0)-catalyzed intramolecular Heck-type reaction of oxime ether has been developed, providing convenient access to heterocyclic oximes.
Co-reporter:Xiaojun Wang;Tong Fang ;Dr. Xiaofeng Tong
Angewandte Chemie 2011 Volume 123( Issue 23) pp:5473-5476
Publication Date(Web):
DOI:10.1002/ange.201100945
Co-reporter:Xiaojun Wang;Tong Fang ;Dr. Xiaofeng Tong
Angewandte Chemie International Edition 2011 Volume 50( Issue 23) pp:5361-5364
Publication Date(Web):
DOI:10.1002/anie.201100945
Co-reporter:Qiongmei Zhang ; Lei Yang
Journal of the American Chemical Society 2010 Volume 132(Issue 8) pp:2550-2551
Publication Date(Web):February 4, 2010
DOI:10.1021/ja100432m
A novel PPh3-catalyzed (4 + n) annulation of 2-(acetoxymethyl)buta-2,3-dienoates 1c−e with 1,n-bisnucleophiles (n = 1, 2) has been developed to provide a facile synthetic method for cyclopentene and 1,2,3,6-tetrahydropyridazine derivatives. The acetate group of 2-(acetoxymethyl)buta-2,3-dienoate is crucial for the formation of 1,4-biselectrophilic intermediate C, which is recognized to be a 1,4-biselectrophile that can react with 1,n-bisnucleophiles. Deuterium studies also suggest that the reaction pathway involves a proton-transfer process.
Co-reporter:Huimin Liu, Qiongmei Zhang, Limin Wang and Xiaofeng Tong
Chemical Communications 2010 vol. 46(Issue 2) pp:312-314
Publication Date(Web):24 Nov 2009
DOI:10.1039/B915825A
PPh3-catalyzed [2 + 2 + 2] annulations between two units of an activated terminal alkyne and one unit of an aryl N-tosylimine have been developed to provide a synthetic method for highly substituted dihydropyridines. On the basis of the mechanism of the [2 + 2 + 2] annulation, PPh3-catalyzed [4 + 2] annulations have also been discovered.
Co-reporter:Chaolong Li, Qiongmei Zhang and Xiaofeng Tong
Chemical Communications 2010 vol. 46(Issue 41) pp:7828-7830
Publication Date(Web):20 Sep 2010
DOI:10.1039/C0CC01966F
A tertiary amine-catalyzed formal (3+n) annulation of 2-(acetoxymethyl)buta-2,3-dienoate with 1,n-binucleophiles has been developed, which provides a facile entry to heterocyclic compounds. The mechanism, involving tandem SN2′–SN2′ substitution and Michael addition, has also been established.
Co-reporter:Xianjie Fang, Junyao Sun and Xiaofeng Tong
Chemical Communications 2010 vol. 46(Issue 21) pp:3800-3802
Publication Date(Web):15 Apr 2010
DOI:10.1039/C001830A
A new strategy for Rh(I)-catalyzed [2+2+2] cycloadditions of 1,6-diynes with potassium (Z)-(2-bromovinyl)trifluoroborate as the third two-atom unit has been realized, which provides a facile entry to polysubstituented benzene derivatives.
Co-reporter:Xianjie Fang, Xiaofeng Tong
Tetrahedron Letters 2010 Volume 51(Issue 2) pp:317-320
Publication Date(Web):13 January 2010
DOI:10.1016/j.tetlet.2009.11.006
A domino sequence of cyclization of 1,6-enyne with 2-bromoarylaldehyde followed by the intramolecular Aldol-condensation has been realized in the presence of 5 mol % of palladium catalyst. This sequence provides a convenient protocol to access polycyclic ring systems with readily available starting materials under simple Pd(0)-catalyzed conditions. The intramolecular Aldol-condensation has been proposed as the key step for the catalytic cycle.
Co-reporter:Qiongmei Zhang, Tong Fang, Xiaofeng Tong
Tetrahedron 2010 66(40) pp: 8095-8100
Publication Date(Web):
DOI:10.1016/j.tet.2010.07.043
Co-reporter:Huimin Liu;QiongMei Zhang;Limin Wang Dr. Dr.
Chemistry - A European Journal 2010 Volume 16( Issue 6) pp:1968-1972
Publication Date(Web):
DOI:10.1002/chem.200902105
Abstract
A new PPh3-catalyzed synthesis of alkyl 2-[aryl(tosylimino)methyl]acrylates from propiolate and N-tosylimine has been developed. Deuterium-labelling experiments show that the reaction mechanism involves several hydrogen-transfer processes, which are not the turnover-limiting step and strongly rely on the nature of the reaction media. The stable phosphonium–enamine zwitterion, which was proven to play an important role in the catalytic cycle, has been isolated and characterised by X-ray analysis.
Co-reporter:Xianjie Fang, Chaolong Li and Xiaofeng Tong
Chemical Communications 2009 (Issue 35) pp:5311-5313
Publication Date(Web):28 Jul 2009
DOI:10.1039/B910532H
A formal [2 + 2 + 2] cycloaddition of a 1,6-enyne with 2-bromophenylboronic acid has been realized to construct a multi-substituted dihydronaphthalene scaffold, in which the direct reductive elimination mechanism of aryl-Rh(III)-Csp3 species has been established to form an aryl-Csp3 bond.
Co-reporter:Xianjie Fang, Chaolong Li and Xiaofeng Tong
Chemical Communications 2009(Issue 35) pp:NaN5313-5313
Publication Date(Web):2009/07/28
DOI:10.1039/B910532H
A formal [2 + 2 + 2] cycloaddition of a 1,6-enyne with 2-bromophenylboronic acid has been realized to construct a multi-substituted dihydronaphthalene scaffold, in which the direct reductive elimination mechanism of aryl-Rh(III)-Csp3 species has been established to form an aryl-Csp3 bond.
Co-reporter:Xianjie Fang, Junyao Sun and Xiaofeng Tong
Chemical Communications 2010 - vol. 46(Issue 21) pp:NaN3802-3802
Publication Date(Web):2010/04/15
DOI:10.1039/C001830A
A new strategy for Rh(I)-catalyzed [2+2+2] cycloadditions of 1,6-diynes with potassium (Z)-(2-bromovinyl)trifluoroborate as the third two-atom unit has been realized, which provides a facile entry to polysubstituented benzene derivatives.
Co-reporter:Chaolong Li, Qiongmei Zhang and Xiaofeng Tong
Chemical Communications 2010 - vol. 46(Issue 41) pp:NaN7830-7830
Publication Date(Web):2010/09/20
DOI:10.1039/C0CC01966F
A tertiary amine-catalyzed formal (3+n) annulation of 2-(acetoxymethyl)buta-2,3-dienoate with 1,n-binucleophiles has been developed, which provides a facile entry to heterocyclic compounds. The mechanism, involving tandem SN2′–SN2′ substitution and Michael addition, has also been established.
Co-reporter:Chen Chen and Xiaofeng Tong
Inorganic Chemistry Frontiers 2014 - vol. 1(Issue 4) pp:
Publication Date(Web):
DOI:10.1039/C4QO00004H
Co-reporter:Huimin Liu, Qiongmei Zhang, Limin Wang and Xiaofeng Tong
Chemical Communications 2010 - vol. 46(Issue 2) pp:NaN314-314
Publication Date(Web):2009/11/24
DOI:10.1039/B915825A
PPh3-catalyzed [2 + 2 + 2] annulations between two units of an activated terminal alkyne and one unit of an aryl N-tosylimine have been developed to provide a synthetic method for highly substituted dihydropyridines. On the basis of the mechanism of the [2 + 2 + 2] annulation, PPh3-catalyzed [4 + 2] annulations have also been discovered.
Co-reporter:Hui Liu, Limin Wang and Xiaofeng Tong
Chemical Communications 2011 - vol. 47(Issue 44) pp:NaN12208-12208
Publication Date(Web):2011/10/03
DOI:10.1039/C1CC15257B
A Pd(0)-catalyzed intramolecular Heck-type reaction of oxime ether has been developed, providing convenient access to heterocyclic oximes.
Co-reporter:Kun Li, Jian Hu, Hui Liu and Xiaofeng Tong
Chemical Communications 2012 - vol. 48(Issue 23) pp:NaN2902-2902
Publication Date(Web):2012/01/23
DOI:10.1039/C2CC30242J
A DABCO-catalyzed (3 + 3) annulation between 2-(acetoxymethyl)buta-2,3-dienoate and sulfur ylides has been developed, which provides a facile method for the synthesis of 4H-pyrans bearing a vinyl sulfide group.