Guo-Qiang Lin

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Name: 林国强; GuoQiang Lin

Organization: Shanghai Institute of Organic Chemistry , China

Department: CAS Key Laboratory of Synthetic Chemistry of Natural Substances

Title: Professor(PhD)

TOPICS

Organic Chemistry

Chemicals
References

Enantioselective Rhodium-Catalyzed Alkenylation of Aliphatic Imines

Co-reporter:Xue-Wei Qian, Ze-Jian Xue, Qian Zhao, Zhe Cui, Ya-Jing Chen, Chen-Guo Feng, and Guo-Qiang Lin

Organic Letters October 20, 2017 Volume 19(Issue 20) pp:5601-5601

Publication Date(Web):October 9, 2017

DOI:10.1021/acs.orglett.7b02737

An efficient, enantioselective rhodium-catalyzed addition of potassium alkenyltrifluoroborates to N-nosyl aliphatic imines has been realized. Good reaction yields and excellent enantioselectivities (94–99% ee) were obtained for a variety of aliphatic imines and nucleophilic alkenyltrifluoroborates. An active rhodium-diene catalyst and the precise reaction condition control proved to be pivotal for success.

Tunable Arylative Cyclization of 1,6-Enynes Triggered by Rhodium(III)-Catalyzed C–H Activation

Co-reporter:Yuki Fukui ; Ping Liu ; Qiang Liu ; Zhi-Tao He ; Nuo-Yi Wu ; Ping Tian

Journal of the American Chemical Society 2014 Volume 136(Issue 44) pp:15607-15614

Publication Date(Web):October 13, 2014

DOI:10.1021/ja5072702

Two tunable arylative cyclizations of cyclohexadienone-containing 1,6-enynes are reported via rhodium(III)-catalyzed C–H activation of O-substituted N-hydroxybenzamides. The use of different O substituents, i.e. O-Piv and O-Me, on the directing group allows the formation of either tetracyclic isoquinolones through an Ⓝ-Michael addition process or hydrobenzofurans through a Ⓒ-Michael addition process. Mechanistic investigations of these two cascade reactions clearly indicated that the C–H bond cleavage process was involved in the turnover-limiting step. Furthermore, the cyclization products could be subjected to various transformations for elaborating the pharmaceutically and synthetically valuable potential. This is the first example of a rhodium(III)-catalyzed arylative cyclization reaction of 1,6-enynes, and the results extend the application realm of Cp*RhIII-catalyzed C–H activation cascade reactions.

Copper-Catalyzed Asymmetric Hydroboration of α-Dehydroamino Acid Derivatives: Facile Synthesis of Chiral β-Hydroxy-α-amino Acids

Co-reporter:Zhi-Tao He, Yi-Shuang Zhao, Ping Tian, Chuan-Chuan Wang, Han-Qing Dong, and Guo-Qiang Lin

Organic Letters 2014 Volume 16(Issue 5) pp:1426-1429

Publication Date(Web):February 14, 2014

DOI:10.1021/ol500219e

The Cu-catalyzed asymmetric conjugate hydroboration reaction of β-substituted α-dehydroamino acid derivatives has been established, affording enantioenriched syn- and anti-β-boronate-α-amino acid derivatives with excellent combined yields (83–99%, dr ≈ 1:1) and excellent enantioselectivities (92–98% ee). The hydroboration products were expediently converted into valuable β-hydroxy-α-amino acid derivatives, which were widely used in the preparation of chiral drugs and bioactive molecules.

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.

Enantioselective Alkenylation of Aldimines Catalyzed by a Rhodium–Diene Complex

Co-reporter:Zhe Cui, Ya-Jing Chen, Wen-Yun Gao, Chen-Guo Feng, and Guo-Qiang Lin

Organic Letters 2014 Volume 16(Issue 3) pp:1016-1019

Publication Date(Web):January 14, 2014

DOI:10.1021/ol5000154

An efficient rhodium-catalyzed asymmetric addition reaction of potassium alkenyltrifluoroborates to N-nosylaldimines has been developed. Under optimal conditions, the reactions proceeded with good to excellent yields and excellent enantioselectivities (97 → 99% ee). The utility of this method is demonstrated by the formal synthesis of (−)-aurantioclavine.

Enantioselective Rhodium-Catalyzed Arylation of Cyclic N-Sulfamidate Alkylketimines: A New Access to Chiral β-Alkyl-β-aryl Amino Alcohols

Co-reporter:Ya-Jing Chen, Ya-Heng Chen, Chen-Guo Feng, and Guo-Qiang Lin

Organic Letters 2014 Volume 16(Issue 12) pp:3400-3403

Publication Date(Web):June 12, 2014

DOI:10.1021/ol501464e

The enantioselective rhodium-catalyzed 1,2-addition of arylboronates to cyclic N-sulfamidate alkylketimines was developed. With a rhodium/diene complex as catalyst, high enantioselectivity and broad functional group tolerance were observed. The resulting sulfamidates can easily be converted into chiral β-alkyl-β-aryl amino alcohols.

Wagner–Meerwein rearrangement of [3.3.1] bicyclic N-Boc aminols: vinyl migration in preference to aryl migration

Co-reporter:Jian-Guo Fu, Rui Ding, Bing-Feng Sun, Guo-Qiang Lin

Tetrahedron 2014 70(44) pp: 8374-8379

Publication Date(Web):

DOI:10.1016/j.tet.2014.08.072

Divergent Total Synthesis of the Lycopodium Alkaloids Huperzine A, Huperzine B, and Huperzine U

Co-reporter:Rui Ding, Jian-Guo Fu, Guang-Qiang Xu, Bing-Feng Sun, and Guo-Qiang Lin

The Journal of Organic Chemistry 2014 Volume 79(Issue 1) pp:240-250

Publication Date(Web):December 3, 2013

DOI:10.1021/jo402419h

Huperzine A, huperzine B, and huperzine U are congeners isolated from the Chinese herb Huperzia serrata (=Lycopodium serratum) in minuscule amounts. The most efficient total synthesis of huperzine A, the first asymmetric total syntheses of huperzine B, and the first total synthesis of huperzine U have been achieved efficiently in overall yields of 17%, 10%, and 9%, respectively, each spanning 10–13 steps from (R)-pulegone. The featured steps include palladium-catalyzed Buchwald–Hartwig coupling and Heck cyclization reactions and an Ir-catalyzed olefin isomerization reaction. This work has established the absolute configurations of huperzine B and huperzine U and revealed that natural huperzine A, huperzine B, and huperzine U possess the same set of absolute stereochemistries, thus providing support for the potential role of huperzine B and huperzine U in the biosynthesis of huperzine A.

A novel and concise synthetic access to chiral 2-substituted-4-piperidone

Co-reporter:Bai-Ling Chen;Bing Wang

Science China Chemistry 2014 Volume 57( Issue 7) pp:945-953

Publication Date(Web):2014 July

DOI:10.1007/s11426-014-5065-3

A novel and concise synthetic access to enantiopure chiral 2-aryl/alkyl substituted 4-piperidone has been demonstrated. This new route features two key steps: the highly diastereoselective conjugate addition of homochiral lithium amides to trans-β-substituted-α,β-unsaturated methyl esters guaranteed the enantiopurity at 2 position (de >19:1) and the intramolecular attacking of carbanions to methyl esters led to the formation of the piperidone ring. A wide range of substrates, including chiral 2-aryl and 2-alkyl-4-piperidones, were successfully synthesized with modest to high yield. Moreover, some non-chiral 3-substituted-4-piperidones were also synthesized with enhanced ring-formation yield, implicating the versatility of this method in construction of various piperidine rings.

Cu-Catalyzed Asymmetric Borylative Cyclization of Cyclohexadienone-Containing 1,6-Enynes

Co-reporter:Ping Liu ; Yuki Fukui ; Ping Tian ; Zhi-Tao He ; Cai-Yun Sun ; Nuo-Yi Wu

Journal of the American Chemical Society 2013 Volume 135(Issue 32) pp:11700-11703

Publication Date(Web):July 26, 2013

DOI:10.1021/ja404593c

The first Cu-catalyzed asymmetric borylative cyclization of cyclohexadienone-containing 1,6-enynes is achieved through a tandem process: selective β-borylation of propargylic ether and subsequent conjugate addition to cyclohexadienone. The reaction proceeds with excellent regioselectivity and enantioselectivity to afford an optically pure cis-hydrobenzofuran framework bearing alkenylboronate and enone substructures. Furthermore, the resulting bicyclic products could be converted to bridged and tricyclic ring structures. This method extends the realm of Cu-catalyzed asymmetric tandem reactions using bis(pinacolato)diboron (B2pin2).

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.

Catalytic Asymmetric Conjugate Addition of -Substituted Nitro Acetates to Nitro Olefins: Enantioselective Synthesis of Highly Substituted -Lactams

Co-reporter:Ying-Zi Li;Fei Li;Ping Tian

European Journal of Organic Chemistry 2013 Volume 2013( Issue 8) pp:1558-1565

Publication Date(Web):

DOI:10.1002/ejoc.201201444

Abstract

Bifunctional bis(demethyldihydroquinine)-catalyzed asymmetric conjugate addition of α-substituted nitro acetates to nitro olefins is described. These addition reactions proceed smoothly with a low catalyst loading (1.0 mol-%) at 0 °C, giving excellent diastereo- (up to 99:1 dr) and enantioselectivities (up to 98 % ee). Furthermore, highly substituted and optically pure 1-pyrazoline and γ-lactam have been prepared to demonstrate the synthetic application of the addition products.

The Special Issue Dedicated to the Memory of Professor Wei-Shan Zhou

Co-reporter:Guo-Qiang Lin;Ran Hong

Chinese Journal of Chemistry 2013 Volume 31( Issue 1) pp:

Publication Date(Web):

DOI:10.1002/cjoc.201390002

No abstract is available for this article.

Stereoselective Total Synthesis of Tubulysin V

Co-reporter:Rui Wang;Ping Tian ;Guoqiang Lin

Chinese Journal of Chemistry 2013 Volume 31( Issue 1) pp:40-48

Publication Date(Web):

DOI:10.1002/cjoc.201200984

Abstract

The total synthesis of tubulysin V was accomplished in 1.0% overall yield with linear 13 steps. Our synthetic strategy featured the following two reactions. One is zinc-mediated aza-Barbier reaction of (R)-N-tert-butanesulfinyl imine 8 with β-ester group functionalized allylic bromide 9 to afford the chiral homo-allylic amine (7); the other is to employ the methodology of aqueous indium-mediated aza-Barbier reaction previously developed by our group, giving the chiral homo-allylic amine 13 with high efficiency.

Collective Total Synthesis of EnglerinA and B, OrientalolE and F, and Oxyphyllol: Application of the Organocatalytic [4+3] Cycloaddition Reaction

Co-reporter:Jie Wang;Shu-Guang Chen;Dr. Bing-Feng Sun; Guo-Qiang Lin; Yong-Jia Shang

Chemistry - A European Journal 2013 Volume 19( Issue 7) pp:2539-2547

Publication Date(Web):

DOI:10.1002/chem.201203467

Abstract

The concise collective total synthesis of englerin A and B, orientalol E and F, and oxyphyllol has been accomplished in 10–15 steps, with the total synthesis of orientalol E and oxyphyllol being achieved for the first time. The success obtained was enabled by the realization of the [4+3] cycloaddition reaction of 9 and 10. Other features of the synthesis include 1) the intramolecular Heck reaction to access the azulene core, 2) the epoxidation–S_N2′ reduction sequence to access the allylic alcohol, 3) the efficient regioselective and stereoselective formal hydration of the bridging CC bond in the synthesis of englerins, and 4) the late-stage chemo- and stereoselective CH oxidation in the synthesis of orientalol E. The total synthesis of these natural products has enabled the structural revision of oxyphyllol and established the absolute stereochemical features of the organocatalytic [4+3] cycloaddition reaction. The identification of 5 as the natural product oxyphyllol, the success in converting 5 to orientalol E, along with the fact that englerins and oxyphyllol were isolated from plants of the same genus Phyllanthus gives support to our proposed biosynthetic pathways. This work may enable detailed biological evaluations of these natural products and their analogues and derivatives, especially of their potential in the fight against renal cell carcinoma (RCC).

An Efficient Total Synthesis of (−)-Huperzine A‡

Co-reporter:Rui Ding, Bing-Feng Sun, and Guo-Qiang Lin

Organic Letters 2012 Volume 14(Issue 17) pp:4446-4449

Publication Date(Web):August 17, 2012

DOI:10.1021/ol301951r

The total synthesis of Lycopodium alkaloid (−)-huperzine A has been accomplished in 10 steps with 17% overall yield from commercially abundant (R)-pulegone. The synthetic route features an efficient synthesis of 4 via a Buchwald–Hartwig coupling reaction, a dianion-mediated highly stereoselective alkylation of 4, and a rare example of an intramolecular Heck reaction of an enamine-type substrate. The stereoselective β-elimination and the accompanying Wagner–Meerwein rearrangement are of particular interest.

An Efficient Total Synthesis of (−)-Epothilone B

Co-reporter:Jie Wang, Bing-Feng Sun, Kai Cui, and Guo-Qiang Lin

Organic Letters 2012 Volume 14(Issue 24) pp:6354-6357

Publication Date(Web):December 7, 2012

DOI:10.1021/ol303148g

An efficient total synthesis of (−)-epothilone B has been achieved in ca. 8% yield over 11 steps from 9 (or 10 steps from 7/8), which features a bissiloxane-tethered ring closing metathesis reaction to approach the trisubstituted (Z) double bond and forms a new basis for further development of an industrial process for epothilone B and ixabepilone.

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.

Easily accessible chiral dicyclopentadiene ligands for rhodium-catalyzed enantioselective 1,4-addition reactions

Co-reporter:Cheng Shao, Hong-Jie Yu, Chen-Guo Feng, Rui Wang, Guo-Qiang Lin

Tetrahedron Letters 2012 Volume 53(Issue 22) pp:2733-2735

Publication Date(Web):30 May 2012

DOI:10.1016/j.tetlet.2012.03.087

A variety of novel C1-symmetric chiral diene ligands based on the dicyclopentadiene (DCP) skeleton were easily prepared from commercially available DCP. The application of these diene ligands in the rhodium-catalyzed asymmetric 1,4-addition of arylboronic acids to α,β-unsaturated carbonyl compounds has been examined and excellent enantioselectivities (up to 97% ee) as well as good yields were achieved under mild reaction conditions.

Highly Enantioselective Alkenylation of Cyclic ,-Unsaturated Carbonyl Compounds as Catalyzed by a RhodiumDiene Complex: Application to the Synthesis of (S)-Pregabalin and ()--Kainic Acid

Co-reporter:Hong-Jie Yu;Cheng Shao;Zhe Cui;Dr. Chen-Guo Feng; Guo-Qiang Lin

Chemistry - A European Journal 2012 Volume 18( Issue 42) pp:13274-13278

Publication Date(Web):

DOI:10.1002/chem.201202660

Rhodium/diene-catalyzed asymmetric arylation of N-Boc-protected α,β-unsaturated δ-lactam with arylboronic acids: enantioselective synthesis of 4-aryl-2-piperidinones

Co-reporter:Zhi-Tao He, Ya-Bing Wei, Hong-Jie Yu, Cai-Yun Sun, Chen-Guo Feng, Ping Tian, Guo-Qiang Lin

Tetrahedron 2012 68(45) pp: 9186-9191

Publication Date(Web):

DOI:10.1016/j.tet.2012.09.001

Mechanistic Investigations of a Palladium-Diene Catalyzed Suzuki–Miyaura Cross-Coupling Reaction

Co-reporter:Xiaoshuang He, Shusheng Zhang, Yinlong Guo, Haoyang Wang, and Guoqiang Lin

Organometallics 2012 Volume 31(Issue 8) pp:2945-2948

Publication Date(Web):March 27, 2012

DOI:10.1021/om300115x

The mechanism of the first example of a palladium diene catalyzed asymmetric Suzuki–Miyaura cross-coupling reaction has been validated, with the key palladium intermediates captured and characterized. The identified species corresponding to each catalytic step were firmly associated with the diene ligand in our observations. In the ESI-MS/MS experiments by CID (collision-induced dissociation), the fragmentation of the gas-phase transmetalation species was consistent with the product-yielding process in the reductive elimination step and thus revealed the catalytically active species of the reaction system.

Asymmetric Synthesis of β-Substituted γ-Lactams via Rhodium/Diene-Catalyzed 1,4-Additions: Application to the Synthesis of (R)-Baclofen and (R)-Rolipram

Co-reporter:Cheng Shao, Hong-Jie Yu, Nuo-Yi Wu, Ping Tian, Rui Wang, Chen-Guo Feng, and Guo-Qiang Lin

Organic Letters 2011 Volume 13(Issue 4) pp:788-791

Publication Date(Web):January 19, 2011

DOI:10.1021/ol103054a

An efficient rhodium/diene-catalyzed asymmetric addition of arylboronic acids to α,β-unsaturated γ-lactams has been developed. The power of this methodology is further demonstrated by the concise synthesis of (R)-baclofen and (R)-rolipram.

Tandem Amination/Cycloisomerization of Aryl Propargylic Alcohols with 2-Aminopyridines as an Expedient Route to Imidazo[1,2-a]pyridines

Co-reporter:Ping Liu;Chun-Lin Deng;Xinsheng Lei

European Journal of Organic Chemistry 2011 Volume 2011( Issue 36) pp:7308-7316

Publication Date(Web):

DOI:10.1002/ejoc.201101053

Abstract

A new tandem route leading to imidazo[1,2-a]pyridines has been explored through the direct amination of aryl propargylic alcohols with 2-aminopyridines and their subsequent intramolecular cycloisomerization. A ZnCl₂/CuCl system has been developed to promote this transformation, which resulted in various imidazo[1,2-a]pyridines in moderate to good yields.

Concise approach to the core of englerin A via an organocatalytic [4+3] cycloaddition reaction

Co-reporter:Bing-Feng Sun, Chao-Lei Wang, Rui Ding, Jin-Yi Xu, Guo-Qiang Lin

Tetrahedron Letters 2011 Volume 52(Issue 17) pp:2155-2158

Publication Date(Web):27 April 2011

DOI:10.1016/j.tetlet.2010.11.087

A concise enantioselective synthesis of diversely functionalized advanced intermediates comprising the tricyclic skeleton of englerin A and related oxygen-bridged guaianes has been successfully accomplished, which features a Harmata organocatalytic [4+3] cycloaddition reaction.

C1-Symmetric Dicyclopentadienes as New Chiral Diene Ligands for Asymmetric Rhodium-Catalyzed Arylation of N-Tosylarylimines

Co-reporter:Cheng Shao, Hong-Jie Yu, Nuo-Yi Wu, Chen-Guo Feng and Guo-Qiang Lin

Organic Letters 2010 Volume 12(Issue 17) pp:3820-3823

Publication Date(Web):August 12, 2010

DOI:10.1021/ol101531r

Monosubstituted C1-symmetric dicyclopentadienes as a new class of diene ligands have been developed for asymmetric arylation of N-tosylarylimines in excellent yields (98−99%) with high enantioselectivities (90−96%). The preparation of these diene ligands relied on an efficient lipase-catalyzed resolution as the key step.

Recent applications of chiral N-tert-butanesulfinyl imines, chiral diene ligands and chiral sulfur–olefin ligands in asymmetric synthesis

Co-reporter:Han-Qing Dong, Ming-Hua Xu, Chen-Guo Feng, Xing-Wen Sun and Guo-Qiang Lin

Inorganic Chemistry Frontiers 2015 - vol. 2(Issue 1) pp:NaN89-89

Publication Date(Web):2014/11/18

DOI:10.1039/C4QO00245H

This review highlights the recent applications of chiral N-tert-butanesulfinyl imines and chiral diene ligands, with bicyclo[3.3.0]octadiene and dicyclopentadiene skeletons, in asymmetric chemical transformations. The chiral sulfinamide–olefin products from allylation of N-tert-butanesulfinyl imines can be used as hybrid ligands for transition metal-catalyzed asymmetric reactions. The efforts in the further exploration of chiral sulfur–olefin ligands are also discussed.

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 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

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