Xing-Wen Sun

Enantioselective synthesis of spirooxindole benzoquinolizines via organo-catalyzed cascade reactions

Co-reporter:Yu Tan;Er-Lu Feng;Qiang-Sheng Sun;Hua Lin;Xun Sun;Guo-Qiang Lin

Organic & Biomolecular Chemistry 2017 vol. 15(Issue 4) pp:778-781

Publication Date(Web):2017/01/25

DOI:10.1039/C6OB02157C

A Michael–Mannich–hemiaminalization–dehydration cascade reaction was developed for the construction of spirooxindole benzoquinolizine derivatives. Additionally, spirooxindole benzoindolizidine was prepared conveniently through a ring-contracted rearrangement reaction from spirooxindole benzoquinolizine.

Asymmetric cinnamylation of N-tert-butanesulfinyl imines with cinnamyl acetates: total syntheses of (+)-lycoricidine and (+)-7-deoxypancratistatin

Co-reporter:Sen-Lin Cai;Bin-Hua Yuan;Yi-Xiang Jiang;Guo-Qiang Lin

Chemical Communications 2017 vol. 53(Issue 25) pp:3520-3523

Publication Date(Web):2017/03/23

DOI:10.1039/C7CC00108H

Highly diastereoselective palladium catalyzed cinnamylation of N-tert-butanesulfinyl imines with cinnamyl acetates has been established to provide enantioenriched β-aryl homoallylic amines. The synthetic application of this stragety has been successfully demonstrated in the concise total syntheses of antitumor natural products (+)-lycoricidine and (+)-7-deoxypancratistatin.

Practical Asymmetric Synthesis of Amathaspiramides B, D, and F

Co-reporter:Sen-Lin Cai, Ran Song, Han-Qing Dong, Guo-Qiang Lin, and Xing-Wen Sun

Organic Letters 2016 Volume 18(Issue 9) pp:1996-1999

Publication Date(Web):April 11, 2016

DOI:10.1021/acs.orglett.6b00588

The practical asymmetric synthesis of amathaspiramides B, D, and F has been accomplished by utilizing an aza-Barbier allylation as the key step to construct the common intermediate with two adjacent stereocenters. A kinetically controlled cyclization to build the challenging thermodynamically less stable 8R-hemiaminal moiety is also important in the synthesis of amathaspiramide D. The route is readily scalable, and gram quantity of the final product D has been prepared.

Highly efficient synthesis of enantioenriched fully-substituted spirocyclohexane oxindoles via a Michael-Michael-aldol cascade reaction

Co-reporter:Qiang-Sheng Sun, Hua Lin, Xun Sun, Xing-Wen Sun

Tetrahedron Letters 2016 Volume 57(Issue 50) pp:5673-5676

Publication Date(Web):14 December 2016

DOI:10.1016/j.tetlet.2016.11.019

•Enantioenriched fully-substituted spirocyclohexane oxindoles were synthesized.•Compounds were bearing six consecutive stereocenters, three quaternary stereocenters.•Excellent stereoselectivities (up to 98% ee, dr > 20:1 in all cases) were obtained.A highly efficient organocatalyzed Michael-Michael-aldol cascade reaction for the construction of enantioenriched spirocyclohexane oxindoles bearing six consecutive stereocenters, up to three quaternary stereocenters, including two consecutive quaternary stereocenters has been achieved in good yields with excellent stereoselectivities under mild conditions.

Dual-organocatalytic Michael/Michael/aldol cascade reaction for the asymmetric construction of fully-substituted cyclohexane

Co-reporter:Qiang-Sheng Sun, Hua Zhu, Hua Lin, Yu Tan, Xiao-Di Yang, Xing-Wen Sun, Xun Sun

Tetrahedron Letters 2016 Volume 57(Issue 51) pp:5768-5770

Publication Date(Web):21 December 2016

DOI:10.1016/j.tetlet.2016.11.033

•Enatiopure fully-substituted cyclohexanes bearing six stereocenters were synthesized.•Low loading dual-organocatalysts were used.•Excellent stereoselectivities (>99% ee, >20:1 dr in all cases) were obtained.An efficient cascade reaction was developed affording fully-substituted cyclohexane bearing six contiguous stereocenters via Michael/Michael/aldol sequence. This reaction was catalyzed by low loading of dual-organocatalyst, H-bond donor squaramide (0.5 mol%) and achiral secondary amine pyrrolidine (10 mol%). Good yields (up to 81%), excellent diastereoselectivities (>20:1 in all cases) and enantioselectivities (>99% in all cases) were obtained for a wide array of Michael acceptors.

A highly practical approach to chiral homoallylic–homopropargylic amines via aza-Barbier reaction

Co-reporter:Bin-Hua Yuan, Zhi-Cheng Zhang, Wen-Jie Liu, Xing-Wen Sun

Tetrahedron Letters 2016 Volume 57(Issue 20) pp:2147-2151

Publication Date(Web):18 May 2016

DOI:10.1016/j.tetlet.2016.03.103

•The first access to chiral homoallylic–homopropargylic amine bearing two contiguous stereocenters.•A novel allylic bromide was illustrated in aza-Barbier reaction.•Enantioenriched 3,4-dihydro-2H-pyrroles was prepared in high efficiency via 5-indo-dig pathway.The first access to chiral homoallylic–homopropargylic amine bearing two contiguous stereocenters has been well accomplished via zinc-promoted aza-Barbier reaction. N-tert-Butanesulfinyl ketimines are well-tolerated substrates, providing the tertiary amines in high yields and with excellent diastereoselectivities. 3,4-Dihydro-2H-pyrroles could be prepared in high efficiency by cyclization of the corresponding amines.

Organocatalyzed asymmetric synthesis and absolute configuration assignment of enantioenriched α-benzylaminocoumarins

Co-reporter:Hua Lin, Yu Tan, Jian-Ming Wu, Xiao-Di Yang, Jun-Hua Chen, Xing-Wen Sun

Tetrahedron Letters 2015 Volume 56(Issue 7) pp:913-917

Publication Date(Web):11 February 2015

DOI:10.1016/j.tetlet.2014.12.138

A cinchona alkaloid catalyzed asymmetric Mannich reaction of 4-hydroxycoumarins and N-p-tolylsulfinylimines was achieved to synthesize enantioenriched α-benzylaminocoumarins in moderate to excellent yields (up to 99%) and with moderate to good enantioselectivities (up to 83% ee). The absolute configuration of the resulting chiral amines was assigned by analysis of computational and experimental electronic circular dichroism (ECD) spectroscopies.

Diastereoselective Allylation of N-tert-Butanesulfinyl Imines: An Asymmetric Synthesis Experiment for the Undergraduate Organic Laboratory

Co-reporter:Xiao-Yang Chen; Li-Sen Sun; Xiang Gao

Journal of Chemical Education 2015 Volume 92(Issue 4) pp:714-718

Publication Date(Web):January 23, 2015

DOI:10.1021/ed500292q

An asymmetric synthetic experiment that encompasses both diastereoselectivity and enantioselectivity is described. In this experiment, Zn-mediated allylation of an (R)-N-tert-butanesulfinyl imine is first performed to obtain either diastereomer using two different solvent systems, followed by oxidation of the homoallylic N-tert-butanesulfinyl amines, which gives either enantiomer of the corresponding products. Purification by flash column chromatography is required at the final step and the desired products are isolated in good overall yields. The diastereomeric ratio (dr) of the allylation products is determined by 1H and 19F NMR spectroscopy, while the enantiomeric excess (ee) of the final products is measured by chiral HPLC. Overall, this experiment can be carried out with readily accessible reagents under mild conditions. Moreover, it enables students to learn the differences between enantiomers and diastereomers, the determination of ee and dr regarding optical compounds using HPLC and NMR spectroscopy, and how a reversal of stereochemical outcome is realized simply by tuning the reaction solvent.

Squaramide-Catalyzed Synthesis of Enantioenriched Spirocyclic Oxindoles via Ketimine Intermediates with Multiple Active Sites

Co-reporter:Qiang-Sheng Sun;Hua Zhu;Yong-Jian Chen;Dr. Xiao-Di Yang; Xing-Wen Sun; Guo-Qiang Lin

Angewandte Chemie International Edition 2015 Volume 54( Issue 45) pp:13253-13257

Publication Date(Web):

DOI:10.1002/anie.201506206

Abstract

A new method for the construction of five-membered spirocyclic oxindoles is based on a Michael–Mannich cascade reaction of a ketimine intermediated catalyzed by a bifunctional quinine-derived squaramide. The desired products were obtained in excellent yields (up to 94 %) and stereoselectivities (up to >20:1 d.r., >99 % ee). A scaled-up variant also proceeded smoothly showing that the one-pot reaction might find application in the synthesis of bioactive-compound libraries.

Inside Cover: Squaramide-Catalyzed Synthesis of Enantioenriched Spirocyclic Oxindoles via Ketimine Intermediates with Multiple Active Sites (Angew. Chem. Int. Ed. 45/2015)

Co-reporter:Qiang-Sheng Sun;Hua Zhu;Yong-Jian Chen;Dr. Xiao-Di Yang; Xing-Wen Sun; Guo-Qiang Lin

Angewandte Chemie International Edition 2015 Volume 54( Issue 45) pp:

Publication Date(Web):

DOI:10.1002/anie.201508485

Squaramide-Catalyzed Synthesis of Enantioenriched Spirocyclic Oxindoles via Ketimine Intermediates with Multiple Active Sites

Co-reporter:Qiang-Sheng Sun;Hua Zhu;Yong-Jian Chen;Dr. Xiao-Di Yang; Xing-Wen Sun; Guo-Qiang Lin

Angewandte Chemie 2015 Volume 127( Issue 45) pp:13451-13455

Publication Date(Web):

DOI:10.1002/ange.201506206

Abstract

A new method for the construction of five-membered spirocyclic oxindoles is based on a Michael–Mannich cascade reaction of a ketimine intermediated catalyzed by a bifunctional quinine-derived squaramide. The desired products were obtained in excellent yields (up to 94 %) and stereoselectivities (up to >20:1 d.r., >99 % ee). A scaled-up variant also proceeded smoothly showing that the one-pot reaction might find application in the synthesis of bioactive-compound libraries.

Innentitelbild: Squaramide-Catalyzed Synthesis of Enantioenriched Spirocyclic Oxindoles via Ketimine Intermediates with Multiple Active Sites (Angew. Chem. 45/2015)

Co-reporter:Qiang-Sheng Sun;Hua Zhu;Yong-Jian Chen;Dr. Xiao-Di Yang; Xing-Wen Sun; Guo-Qiang Lin

Angewandte Chemie 2015 Volume 127( Issue 45) pp:

Publication Date(Web):

DOI:10.1002/ange.201508485

A highly efficient asymmetric synthesis of quaternary stereocenter-containing indolizidine and quinolizidine alkaloids using aldehydes, nitroalkenes, and unactivated cyclic ketimines

Co-reporter:Yu Tan, Yong-Jian Chen, Hua Lin, Han-Lin Luan, Xing-Wen Sun, Xiao-Di Yang and Guo-Qiang Lin

Chemical Communications 2014 vol. 50(Issue 100) pp:15913-15915

Publication Date(Web):30 Oct 2014

DOI:10.1039/C4CC07703B

A highly efficient approach for the construction of indolizidines and quinolizidines bearing a bridged quaternary stereocenter has been established in a one-pot fashion using aldehydes, nitroalkenes, and cyclic ketimines with excellent enantioselectivities and in high yields. Moreover, this method could be applied to the synthesis of indolizidines in the gram scale.

Dual-Organocatalyst-Promoted Asymmetric Cascade Reaction: Highly Efficient Construction of Enantiopure Fully Substituted Tetrahydro-1,2-oxazines

Co-reporter:Hua Lin, Xing-Wen Sun, and Guo-Qiang Lin

Organic Letters 2014 Volume 16(Issue 3) pp:752-755

Publication Date(Web):January 13, 2014

DOI:10.1021/ol403463h

A four-component asymmetric α-aminoxylation/aza-Michael/Mannich cascade reaction for the construction of fully substituted chiral tetrahydro-1,2-oxazine derivatives was accomplished in high yields with excellent enantio- and diastereoselectivities under mild conditions. The 1,2-oxazine derivative could be transformed to the corresponding multifunctional chiral amino alcohol by N–O cleavage and fused-tricyclic 4-amino-substituted tetrahydroquinolines in good yields with excellent stereoselectivities followed by a Friedel–Crafts reaction. Also a 4-alkoxy-substituted tetrahydroquinoline was achieved by C-4 inversion of a 4-amino-substituted tetrahydroquinoline.

Novel one-pot asymmetric cascade approach toward densely substituted enantioenriched α-methylene-γ-lactams

Co-reporter:Yu Tan, Xiao-Di Yang, Wen-Jie Liu, Xing-Wen Sun

Tetrahedron Letters 2014 Volume 55(Issue 44) pp:6105-6108

Publication Date(Web):29 October 2014

DOI:10.1016/j.tetlet.2014.09.045

A novel one-pot asymmetric synthesis of densely substituted α-methylene-γ-lactams in favor of cis-isomer involving Zn-promoted aza-Barbier-type reaction has been well established. A wide array of α-methylene-γ-lactams were obtained in high yields with excellent diastereomeric ratios from 98:2 to >99:1 and good enantioselectivities. The synthetic potential of such α-methylene-γ-lactams was demonstrated by successfully oxidizing the phenol moiety to quinone in quantitative yield.

An eco-benign and highly efficient access to 3-heterocyclic-substituted isoindolinones in ammonia water

Co-reporter:Shao-Chun Shen, Xing-Wen Sun and Guo-Qiang Lin

Green Chemistry 2013 vol. 15(Issue 4) pp:896-900

Publication Date(Web):25 Feb 2013

DOI:10.1039/C3GC40162F

A highly efficient three-component reaction of 2-formyl benzoic acid, ammonia and 4-hydroxycoumarin or indole in water was developed. With this highly environmentally benign protocol, a series of isoindolinone derivatives were efficiently produced in good to excellent yields.

Highly efficient asymmetric construction of quaternary carbon-containing homoallylic and homopropargylic amines

Co-reporter:Tao Guo, Ran Song, Bin-Hua Yuan, Xiao-Yang Chen, Xing-Wen Sun and Guo-Qiang Lin

Chemical Communications 2013 vol. 49(Issue 47) pp:5402-5404

Publication Date(Web):23 Apr 2013

DOI:10.1039/C3CC42481B

A highly efficient method for the asymmetric synthesis of chiral quaternary carbon-containing homoallylic and homopropargylic amines under mild conditions was achieved with good yields and high diastereoselectivities.

A highly efficient access to enantiopure tetrahydropyridines: dual-organocatalyst-promoted asymmetric cascade reaction

Co-reporter:Hua Lin, Yu Tan, Wen-Jie Liu, Zhi-Cheng Zhang, Xing-Wen Sun and Guo-Qiang Lin

Chemical Communications 2013 vol. 49(Issue 38) pp:4024-4026

Publication Date(Web):21 Mar 2013

DOI:10.1039/C3CC40690C

A highly efficient cascade process of Michael–aza-Henry–hemiaminalization–dehydration was established for the construction of enantiopure tetrahydropyridines using the combination of prolinol trimethylsilyl ether and cinchona alkaloid catalysts. This new approach allowed for the application of aliphatic imines, generated in situ from aldehydes and amines. Good yields (up to 90%), high enantio- (up to >99% ee) and diastereoselectivities (>99:1 d.r. in all cases) were achieved for a broad spectrum of substrates under mild conditions.

A convenient synthesis of chiral vinyl aziridines via aza-Barbier–Darzen type reaction

Co-reporter:Wen-Jie Liu, Yun-Hui Zhao, Xing-Wen Sun

Tetrahedron Letters 2013 Volume 54(Issue 28) pp:3586-3590

Publication Date(Web):10 July 2013

DOI:10.1016/j.tetlet.2013.04.046

A facile and efficient approach for the synthesis of chiral vinyl aziridines has been developed in moderate yields and high diastereoselectivities via Zn-promoted aza-Barbier–Darzen type reaction of (R)-N-tert-butanesulfinyl imines with 1,3-dibromoprop-1-ene.Figure optionsDownload full-size imageDownload as PowerPoint slide

Highly Efficient Asymmetric Synthesis of Enantiopure Dihydro-1,2-oxazines: Dual-Organocatalyst-Promoted Asymmetric Cascade Reaction

Co-reporter:Hua Lin, Yu Tan, Xing-Wen Sun, and Guo-Qiang Lin

Organic Letters 2012 Volume 14(Issue 15) pp:3818-3821

Publication Date(Web):July 18, 2012

DOI:10.1021/ol301218x

A one-pot dual-organocatalyst-promoted asymmetric α-aminoxylation/aza-Michael/aldol consendation cascade reaction is presented. The targeted optically active 1,2-oxazine derivatives are synthesized in moderate yields (up to 70%), excellent enantioselectivities (ee >99% in all cases), and excellent diastereoselectivities (dr up to >99:1) under mild conditions. To further elucidate the synthetic utility of the cascade products, cleavage of the N–O bond is demonstrated and an enantiopure syn-1,4-amino alcohol derivative is achieved in excellent yield.

Highly Efficient Synthesis of Unsymmetrical 3,3-Bis(1H-indol-3-yl)methanes in Water

Co-reporter:Hua Lin;Yang Zang;Xingwen Sun;Guoqiang Lin

Chinese Journal of Chemistry 2012 Volume 30( Issue 10) pp:2309-2314

Publication Date(Web):

DOI:10.1002/cjoc.201200496

Abstract

A simple and practical approach for the preparation of unsymmetric bis(indolyl)methanes (BIMs) was realized by Lewis acid InBr₃-catalyzed Friedel-Crafts reaction of indoles with 3-indolyl-substituted phthalides in water.

Highly efficient asymmetric construction of quaternary carbon-containing homoallylic and homopropargylic amines

Co-reporter:Tao Guo, Ran Song, Bin-Hua Yuan, Xiao-Yang Chen, Xing-Wen Sun and Guo-Qiang Lin

Chemical Communications 2013 - vol. 49(Issue 47) pp:NaN5404-5404

Publication Date(Web):2013/04/23

DOI:10.1039/C3CC42481B

A highly efficient method for the asymmetric synthesis of chiral quaternary carbon-containing homoallylic and homopropargylic amines under mild conditions was achieved with good yields and high diastereoselectivities.

A highly efficient access to enantiopure tetrahydropyridines: dual-organocatalyst-promoted asymmetric cascade reaction

Co-reporter:Hua Lin, Yu Tan, Wen-Jie Liu, Zhi-Cheng Zhang, Xing-Wen Sun and Guo-Qiang Lin

Chemical Communications 2013 - vol. 49(Issue 38) pp:NaN4026-4026

Publication Date(Web):2013/03/21

DOI:10.1039/C3CC40690C

A highly efficient cascade process of Michael–aza-Henry–hemiaminalization–dehydration was established for the construction of enantiopure tetrahydropyridines using the combination of prolinol trimethylsilyl ether and cinchona alkaloid catalysts. This new approach allowed for the application of aliphatic imines, generated in situ from aldehydes and amines. Good yields (up to 90%), high enantio- (up to >99% ee) and diastereoselectivities (>99:1 d.r. in all cases) were achieved for a broad spectrum of substrates under mild conditions.

A highly efficient asymmetric synthesis of quaternary stereocenter-containing indolizidine and quinolizidine alkaloids using aldehydes, nitroalkenes, and unactivated cyclic ketimines

Co-reporter:Yu Tan, Yong-Jian Chen, Hua Lin, Han-Lin Luan, Xing-Wen Sun, Xiao-Di Yang and Guo-Qiang Lin

Chemical Communications 2014 - vol. 50(Issue 100) pp:NaN15915-15915

Publication Date(Web):2014/10/30

DOI:10.1039/C4CC07703B

A highly efficient approach for the construction of indolizidines and quinolizidines bearing a bridged quaternary stereocenter has been established in a one-pot fashion using aldehydes, nitroalkenes, and cyclic ketimines with excellent enantioselectivities and in high yields. Moreover, this method could be applied to the synthesis of indolizidines in the gram scale.

Asymmetric synthesis of poly-substituted spirocyclohexane oxindole via a squaramide catalyzed cascade Michael–Michael–aldol sequence

Co-reporter:Qiang-Sheng Sun, Xiao-Yang Chen, Hua Zhu, Hua Lin, Xing-Wen Sun and Guo-Qiang Lin

Inorganic Chemistry Frontiers 2015 - vol. 2(Issue 2) pp:NaN113-113

Publication Date(Web):2014/12/30

DOI:10.1039/C4QO00299G

A squaramide-catalyzed Michael–Michael–aldol cascade sequence of three readily accessible substrates (1,3-dicarbonyl compound, nitroalkene and methyleneindolinone) was developed. The reactions led to a series of enantioenriched spirocyclohexane oxindoles bearing six contiguous stereocenters in good yields (up to 85%) and with excellent stereoselectivities (>20:1 dr, >99% ee).

Asymmetric cinnamylation of N-tert-butanesulfinyl imines with cinnamyl acetates: total syntheses of (+)-lycoricidine and (+)-7-deoxypancratistatin

Co-reporter:Sen-Lin Cai, Bin-Hua Yuan, Yi-Xiang Jiang, Guo-Qiang Lin and Xing-Wen Sun

Chemical Communications 2017 - vol. 53(Issue 25) pp:NaN3523-3523

Publication Date(Web):2017/02/20

DOI:10.1039/C7CC00108H

Highly diastereoselective palladium catalyzed cinnamylation of N-tert-butanesulfinyl imines with cinnamyl acetates has been established to provide enantioenriched β-aryl homoallylic amines. The synthetic application of this stragety has been successfully demonstrated in the concise total syntheses of antitumor natural products (+)-lycoricidine and (+)-7-deoxypancratistatin.

Enantioselective synthesis of spirooxindole benzoquinolizines via organo-catalyzed cascade reactions

Co-reporter:Yu Tan, Er-Lu Feng, Qiang-Sheng Sun, Hua Lin, Xun Sun, Guo-Qiang Lin and Xing-Wen Sun

Organic & Biomolecular Chemistry 2017 - vol. 15(Issue 4) pp:NaN781-781

Publication Date(Web):2016/10/27

DOI:10.1039/C6OB02157C

A Michael–Mannich–hemiaminalization–dehydration cascade reaction was developed for the construction of spirooxindole benzoquinolizine derivatives. Additionally, spirooxindole benzoindolizidine was prepared conveniently through a ring-contracted rearrangement reaction from spirooxindole benzoquinolizine.

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