Ying Cheng

Chiral N-heterocyclic carbene/Lewis acid cooperative catalysis of the reaction of 2-aroylvinylcinnamaldehydes: a switch of the reaction pathway by Lewis acid activation

Co-reporter:Zhan-Yong Wang, Ya-Li Ding, Gang Wang and Ying Cheng

Chemical Communications 2016 vol. 52(Issue 4) pp:788-791

Publication Date(Web):06 Nov 2015

DOI:10.1039/C5CC08866F

The chiral N-heterocyclic carbene/Lewis acid co-catalyzed reaction of 2-aroylvinylcinnamaldehydes produced good yields of indeno[1,2-c]furan-1-one derivatives with excellent enantioselectivity and diastereoselectivity. A switch of intramolecular cyclization to intermolecular dimerization was achieved by the cooperative catalysis of chiral triazole carbene and Ti(OPr-i)4 catalysts.

The Reaction of 2-Aroylvinylcinnamaldehydes with Aromatic Aldehydes by Dual Catalysis with a Chiral N-Heterocyclic Carbene and a Lewis Acid: Enantioselective Construction of Tetrahydroindeno[1,2-c]furan-1-ones

Co-reporter:Gang Wang, Zhan-Yong Wang, Shuang-Shuo Niu, Yin Rao, and Ying Cheng

The Journal of Organic Chemistry 2016 Volume 81(Issue 18) pp:8276-8286

Publication Date(Web):August 22, 2016

DOI:10.1021/acs.joc.6b01362

The cooperative chiral N-heterocyclic carbene and Lewis acid catalyzed reactions between 2-aroylvinylcinnamaldehydes and various aromatic aldehydes produced multifunctional tetrahydroindeno[1,2-c]furan-1-ones with excellent enantioselectivity. This work developed a versatile and efficient method for highly enantioselective construction of chiral tetrahydroindeno[1,2-c]furan-1-one, which are not easily prepared by other synthetic methods.

N-Heterocyclic Carbene/Lewis Acid Dual Catalysis for the Divergent Construction of Enantiopure Bridged Lactones and Fused Indenes

Co-reporter:Zhan-Yong Wang, Ya-Li Ding, Shi-Ning Li, and Ying Cheng

The Journal of Organic Chemistry 2016 Volume 81(Issue 23) pp:11871-11881

Publication Date(Web):November 4, 2016

DOI:10.1021/acs.joc.6b02329

The chiral triazole carbene and Ti(OPr-i)4 cocatalyzed reaction between α,β-unsaturated aldehydes and 2-(aroylvinyl)benzaldehydes was systematically studied. A divergence in reaction pathways was observed under different reaction conditions. In benzene solvent and at ambient temperature, the reaction produced 4,5-dihydro-1,4-methanobenzo[c]oxepin-3-ones, the bridged caprolactones, as the major products in moderate yields with excellent enantioselectivity. The same reaction in dichloroethane and at 50 °C, however, gave 2,8-dihydrocyclopenta[a]indenes as the major products in most cases. The application of the method developed was demonstrated by the transformation of the bridged lactone products into enantiopure 4-hydroxy-1,2,3,4-tetrahydronaphthalene-2-carboxylic acids.

N-Heterocyclic Carbene-Catalyzed Oxidative Annulations of α,β-Unsaturated Aldehydes with Hydrazones: Selective Synthesis of Optically Active 4,5-Dihydropyridazin-3-ones and Pyridazin-3-ones

Co-reporter:Jian-Hui Mao, Zi-Tian Wang, Zhan-Yong Wang, and Ying Cheng

The Journal of Organic Chemistry 2015 Volume 80(Issue 12) pp:6350-6359

Publication Date(Web):May 27, 2015

DOI:10.1021/acs.joc.5b00784

A novel and efficient method for the highly enantioselective synthesis of chiral 4,5-dihydropyridazin-3-one derivatives has been developed based on the chiral N-heterocyclic carbene-catalyzed oxidative annulation between α,β-unsaturated aldehydes and hydrazones. Meanwhile, the selective synthesis of either 4,5-dihydropyridazin-3-ones or pyridazin-3-one derivatives from the same reactants has been achieved by simply varying catalytic and reaction conditions.

N-Heterocyclic Carbene-Catalyzed Diastereoselective and Enantioselective Reaction of 2-Aroylvinylcinnamaldehydes with α,β-Unsaturated Imines: Complete Control and Switch of Diastereoselectivity by N-Substituents of Catalysts

Co-reporter:Zi-Tian Wang, Yuan Zhao, Zhan-Yong Wang, and Ying Cheng

The Journal of Organic Chemistry 2015 Volume 80(Issue 3) pp:1727-1734

Publication Date(Web):January 13, 2015

DOI:10.1021/jo502668c

Highly diastereoselective and enantioselective reactions between 2-aroylvinylcinnamaldehydes and α,β-unsaturated imines were achieved under asymmetric catalysis of chiral triazole carbene catalysts. In the presence of N-anisylindeno[2,1-b]triazolo[4,3-d][1,4]oxazinium salt, the reaction of 2-aroylvinylcinnamaldehydes with α,β-unsaturated imines afforded indeno[2,1-c]pyran-1-one derivatives 4 with 90%–99% ee, while enantiopure indenocyclopentan-1-ones 5 (>99% ee) were obtained under the catalysis of N-mesitylindeno[2,1-b]triazolo[4,3-d][1,4]oxazinium salt. A slight variation of an N-substituent on triazole carbenes was found to switch completely the diastereoselectivity of the reaction for the formation of indeno[2,1-c]pyran-1-ones.

Changing Reaction Pathways of the Dimerization of 2-Formylcinnamates by N-Heterocyclic Carbene/Lewis Acid Cooperative Catalysis: An Unusual Cleavage of the Carbon–Carbon Bond

Co-reporter:Hai-Yan Dang, Zi-Tian Wang, and Ying Cheng

Organic Letters 2014 Volume 16(Issue 21) pp:5520-5523

Publication Date(Web):October 20, 2014

DOI:10.1021/ol502791s

Catalyzed by a triazole carbene, the dimerization of 2-formylcinnamates underwent benzoin condensation followed by intramolecular oxa-Michael addition to afford isochromeno[4,3-c]isochromene products. Under the catalysis of a combination of triazole carbene and Ti(OPr-i)4 catalysts, the dimerization reaction of 2-formylcinnamates proceeded through a completely different route to furnish the formation of isochromenone derivatives with the elimination of an acetate moiety.

N-Heterocyclic Carbene/Brnsted Base Cascade Catalysis: Base-Controlled Selective Synthesis of Multifunctional Benzofuran-3-ones or Flavone Derivatives from the Reaction of 3-(2-Formylphenoxy)propenoates with Imines

Co-reporter:Yuan Zhao;Zi-Tian Wang

Advanced Synthesis & Catalysis 2014 Volume 356( Issue 11-12) pp:2580-2590

Publication Date(Web):

DOI:10.1002/adsc.201400331

N-Heterocyclic carbene-catalyzed cascade reaction of 2-aroylvinylcinnamaldehydes with 2-aroylvinylchalcones: rapid assembly of six contiguous stereogenic centers with high diastereoselectivity

Co-reporter:Xing-Wen Fan and Ying Cheng

Organic & Biomolecular Chemistry 2014 vol. 12(Issue 1) pp:123-131

Publication Date(Web):10 Oct 2013

DOI:10.1039/C3OB41656A

N-Heterocyclic carbene-catalyzed reaction of 2-aroylvinylcinnamaldehydes with 2-aroylvinylchalcones proceeded via a triple Michael addition and intramolecular lactonization cascade to produce novel 9-(2-aroyl-3-aroylmethyl-1-indanyl)-3-arylindeno[2,1-c]pyran-1-ones in good yields with high diastereoselectivity. This reaction constructed six contiguous stereogenic centers in a single reactive event. Among 32 possible diastereoisomers that contain six stereocenters, only two diastereoisomers were detected with diastereomeric ratios being 10:1–28:1. This work opens up a new avenue for the synthesis of complex indane derivatives, a type of compound that has been reported to possess various biological and pharmaceutical activities.

Changing the Reaction Pathway by NHC/Brønsted Base Cooperative Catalysis: Highly Stereoselective Synthesis of Multifunctional Benzo[a]fluoren-11-ones from the Dimerization of 2-(Aroylvinyl)arylaldehydes

Co-reporter:Yuan-feng Tong, Jian-hui Mao, Song Wu, Yuan Zhao, and Ying Cheng

The Journal of Organic Chemistry 2014 Volume 79(Issue 5) pp:2075-2081

Publication Date(Web):February 7, 2014

DOI:10.1021/jo4027758

The unprecedented NHC/Brønsted base-cocatalyzed dimerization reaction of 2-(aroylvinyl)arylaldehydes was reported. In the presence of a triazole carbene catalyst alone, no reaction of 2-(aroylvinyl)arylaldehydes was observed. However, the combination of triazole carbene and 4-methoxyphenolate efficiently catalyzed the dimerization of 2-(aroylvinyl)arylaldehydes to proceed through a benzoin–Michael–Michael reaction cascade, producing 6-aroyl-5-(aroylmethyl)-11a-hydroxybenzo[a]fluoren-11-ones as the sole diastereomers in good yields.

The reaction of β-lactam carbenes with 3,6-di(2-pyrimidinyl)tetrazine: regulating products by reaction conditions

Co-reporter:Cai-Xia Yan, Yuan Zhao, Xiao-Rong Wang, Ying Cheng

Tetrahedron 2013 69(48) pp: 10279-10283

Publication Date(Web):

DOI:10.1016/j.tet.2013.10.034

A versatile method for the synthesis of heterocyclic ring-fused 1,2-oxazinones from the NHC-catalyzed reactions of 2-aroylvinylarylaldehydes with nitrosoarenes

Co-reporter:Jing Qu, Ying Cheng

Tetrahedron 2013 69(2) pp: 888-894

Publication Date(Web):

DOI:10.1016/j.tet.2012.10.089

N-Heterocyclic carbene-catalyzed cascade annulation reaction of o-vinylarylaldehydes with nitrosoarenes: one-step assembly of functionalized 2,3-benzoxazin-4-ones

Co-reporter:Zhong-Xin Sun and Ying Cheng

Organic & Biomolecular Chemistry 2012 vol. 10(Issue 20) pp:4088-4094

Publication Date(Web):21 Mar 2012

DOI:10.1039/C2OB25137J

The NHC-catalyzed reactions of ortho electron-deficient vinyl substituted arylaldehydes with nitrosoarenes were studied. The reactions produced multifunctional 2,3-benzoxazin-4-ones in good to excellent yields via a cascade aza-benzoin reaction between aldehyde and nitroso groups followed by an intramolecular oxo-Michael addition. The resulting 1-acetate substituted 2,3-benzoxazinones were transformed into a new type of β-hydroxycarboxylate derivatives or 3-oxo-1-isobenzofuranacetates, respectively, under different reductive conditions. This work not only provides a simple and efficient method for the construction of multifunctional 2,3-benzoxazin-4-ones of potential pharmacological interest, but also expands the application of NHC-catalyzed cascade reactions in the formation of carbon–heteroatom and heteroatom–heteroatom bonds.

NHC Brønsted base-catalyzed transformations of isochromene derivatives: regulation of products by the structures of carbene catalysts

Co-reporter:Xing-Wen Fan and Ying Cheng

Organic & Biomolecular Chemistry 2012 vol. 10(Issue 45) pp:9079-9084

Publication Date(Web):09 Oct 2012

DOI:10.1039/C2OB26622A

Two different transformations of α-(isochromen-1-yl)ketones catalyzed by NHC Brønsted bases are reported. In the presence of a triazole carbene, α-(isochromen-1-yl)ketones isomerized into β-(2-(aroylmethylene)phenyl)-α,β-unsaturated ketones in 38–88% yields, while the same reaction catalyzed by an imidazole carbene produced 1-aroylnaphthalene derivatives in 90–99% yields. This work not only provides a new method for the synthesis of a novel type of α,β-unsaturated ketone and multi-substituted naphthalene derivatives, but also advances the application of NHC catalysts in the field of Brønsted base-catalysis.

The reaction of β-lactam carbenes with 3,6-dipyridyltetrazines: switch of reaction pathways by 2-pyridyl and 4-pyridyl substituents of tetrazines

Co-reporter:Xiao-Rong Wang, Juan Xing, Cai-Xia Yan and Ying Cheng

Organic & Biomolecular Chemistry 2012 vol. 10(Issue 5) pp:970-977

Publication Date(Web):26 Oct 2011

DOI:10.1039/C1OB06595E

The reactions of β-lactam carbenes with both 3,6-di(2-pyridyl)tetrazine and 3,6-di(4-pyridyl)tetrazine were studied. It was found that β-lactam carbenes reacted with 3,6-di(2-pyridyl)tetrazine to produce 5-triazolo[1,5-a]pyridylpyrrol-2-ones in good yields, while with 3,6-di(4-pyridyl)tetrazine, they afforded pyrido[c]cyclopenta[b]pyrrol-2-ones in moderate yields. Both reactions were proposed to follow cascade mechanisms containing a 3,6a-dipyridylpyrrolo[3,2-c]pyrazol-5-one intermediate. The different pathways of the transformation of pyrrolo[3,2-c]pyrazol-5-ones were switched by the 2- and 4-pyridyl substituents. This work not only provided a simple and efficient strategy for the construction of novel triazolo[1,5-a]pyridine and pyrido[c]cyclopenta[b]pyrrole derivatives, respectively, but also revealed two different thermal transformation patterns of 3H-pyrazole compounds.

One-Step Formation both of CN and of CO Bonds of N-Alkoxyamides through NHC-Catalyzed Three-Component Reactions of Enals, Nitrosoarenes, and Enones

Co-reporter:Zhong-Xin Sun

European Journal of Organic Chemistry 2012 Volume 2012( Issue 26) pp:4982-4987

Publication Date(Web):

DOI:10.1002/ejoc.201200525

Abstract

NHC-catalyzed three-component reactions of α,β-unsaturated aldehydes (enals), nitrosoarenes, and α,β-unsaturated ketones (enones) were studied. The reactions proceeded through a cascade aza-benzoin condensation/oxo-Michael addition sequence to produce N,O-bisfunctionalized N-hydroxylacrylamides in moderate to good yields. This work not only provides an efficient method for the one-step formation both of the C–N and of the C–O bonds in N-alkoxyamides, but also advances the application of NHC organocatalysis in the field of multicomponent reactions.

The multicomponent reaction of imidazo[1,5-a]pyridine carbenes with phthalaldehydes and dimethyl acetylenedicarboxylate: a facile construction of benzo[d]furo[3,2-b]azepines

Co-reporter:Huan-Rui Pan, Xiao-Rong Wang, Cai-Xia Yan, Zhong-Xin Sun and Ying Cheng

Organic & Biomolecular Chemistry 2011 vol. 9(Issue 7) pp:2166-2174

Publication Date(Web):16 Dec 2010

DOI:10.1039/C0OB00746C

A study on the multicomponent reaction comprising both N-heterocyclic carbenes and substituted phthalaldehydes is reported. The imidazo[1,5-a]pyridine carbenes, namely imidazo[1,5-a]pyridine-3-ylidenes, reacted with phthalaldehydes and DMAD under very mild conditions to produce novel fused tricyclic benzo[d]furo[3,2-b]azepine derivatives. The resulting fused heterocyclic compounds are fluorescent and they give an emission around 500 nm with quantum yields (ΦF) being up to 0.81. This study provides not only a unique approach to fused azepine derivatives that are not easily accessible by other methods, but also opens a new avenue to complicated molecular skeletons. The fluorescence properties of long emission wavelength and high fluorescence quantum yields of some products predict their potential applications as optical sensors.

Reaction of β-Lactam Carbenes with 2-Pyridyl Isonitriles: A One-Pot Synthesis of 2-Carbonyl-3-(pyridylamino)imidazo[1,2-a]pyridines Useful as Fluorescent Probes for Mercury Ion

Co-reporter:Na Shao, Guang-Xian Pang, Cai-Xia Yan, Gao-Feng Shi, and Ying Cheng

The Journal of Organic Chemistry 2011 Volume 76(Issue 18) pp:7458-7465

Publication Date(Web):August 8, 2011

DOI:10.1021/jo201273p

The one-pot reaction of β-lactam carbenes with 2-pyridyl isonitriles followed by an acidic hydrolysis was reported, which produced 2-carbonyl-3-(pyridylamino)imidazo[1,2-a]pyridines in moderate to good yields. Among the resulting novel imidazo[1,2-a]pyridine derivatives, 1-(6-chloro-3-(5-chloropyridin-2-ylamino)imidazo[1,2-a]pyridin-2-yl)-2-ethylbutan-1-one was demonstrated to be an efficient fluorescent probe for mercury ion both in acetonitrile and in buffered aqueous solution.

N-Heterocyclic Carbene Catalyzed Reaction of Phthalaldehydes: Controllable Stereoselective Synthesis of Polyhydroxylated Spiro- and Fused Indenones Dictated by the Structure of NHC Catalysts

Co-reporter:Ying Cheng, Jiang-Hua Peng, Yong-Jia Li, Xun-Yu Shi, Ming-Sheng Tang, and Tian-Yu Tan

The Journal of Organic Chemistry 2011 Volume 76(Issue 6) pp:1844-1851

Publication Date(Web):February 22, 2011

DOI:10.1021/jo102582a

The N-heterocyclic carbene catalyzed stereoselective dimerization reactions of phthalaldehydes produced polyhydroxylated spiro- or fused indenones. The reaction pathways were dictated by the structures of NHC catalysts. Under the catalysis of a imidazole carbene, phthalaldehydes produced dihydroxylspiro[indene-2,1′-isobenzofuran]-3-ones in good to excellent yields, whereas a triazole carbene catalyzed reaction of phthalaldehydes afforded fully cis-trihydroxylindeno[2,1-a]inden-5-ones in high yields. This work not only provides a highly efficient method for the construction of valuable polyhydroxyl substituted indene derivatives that are not easily assembled by other synthetic means but also reflects the versatility of organocatalysis using N-heterocyclic carbenes.

Interaction of β-Lactam Carbenes with 3,6-Diphenyltetrazines: A Five-Step Cascade Reaction for the Direct Construction of Indeno[2,1-b]pyrrol-2-ones

Co-reporter:Juan Xing, Xiao-Rong Wang, Cai-Xia Yan, and Ying Cheng

The Journal of Organic Chemistry 2011 Volume 76(Issue 11) pp:4746-4752

Publication Date(Web):May 6, 2011

DOI:10.1021/jo200499u

A study of the nucleophilic addition of β-lactam carbenes to 3,6-diphenyltetrazines is reported. Instead of the formation of pyrazole derivatives like most reactions between nucleophilic or ambiphilic carbenes and 3,6-disubstituted tetrazines, β-lactam carbenes reacted with 3,6-diphenyltetrazines to produce indeno[2,1-b]pyrrol-2-ones in good yields. The reaction proceeds most probably through a five-step cascade process. This work has not only provided a one-pot operation for the efficient construction of mutisubstituted indeno[2,1-b]pyrrol-2-ones but also revealed the nucleophilicity of β-lactam carbenes.

Dimerization of 2-pyridylisonitriles produces π-extended fused heteroarenes useful as highly selective colorimetric and optical probes for copper ion

Co-reporter:Na Shao, Guang-Xian Pang, Xiao-Rong Wang, Rui-Juan Wu, Ying Cheng

Tetrahedron 2010 66(36) pp: 7302-7308

Publication Date(Web):

DOI:10.1016/j.tet.2010.06.096

Synthesis of novel synthetic intermediates from the reaction of benzimidazole and triazole carbenes with ketenimines and their application in the construction of spiro-pyrroles

Co-reporter:Jun-Ming Mo, Yang-Guang Ma and Ying Cheng

Organic & Biomolecular Chemistry 2009 vol. 7(Issue 23) pp:5010-5019

Publication Date(Web):14 Oct 2009

DOI:10.1039/B915215F

2-(2-Alkoxycarbonyl-1-arylamino-1-propenyl)benzimidazolium and 5-(2-alkoxycarbonyl-1-arylamino-1-propenyl)triazolium salts were synthesized in good yields from the reaction of benzimidazole and triazole carbenes with ketenimines. Upon treatment with a base, both salts were converted into novel 1,3-dipoles which underwent [3+2] cycloaddition reactions with electron-deficient alkynes and allenes to produce benzimidazole-spiro-pyrroles or triazole-spiro-pyrroles. This work provides novel synthons for the construction of multifunctional spiro-pyrrole derivatives that are not easy accessible by other synthetic methods and are potentially amenable to further transformations.

The [3 + 2] cycloaddition reaction of thiazole carbene-derived C-C-Se 1,3-dipoles: a concise and highly efficient strategy for the construction of multifunctional dihydroselenophenes and selenopheno[2,3-b]pyrazines

Co-reporter:Jian-Hong Zhang and Ying Cheng

Organic & Biomolecular Chemistry 2009 vol. 7(Issue 16) pp:3264-3270

Publication Date(Web):29 Jun 2009

DOI:10.1039/B904575A

The first study on the reaction of C+-C-Se− 1,3-dipoles with electron-deficient alkenes and alkyne is reported. 2-Arylselenocarbamoylthiazolium inner salts, the unique thiazole carbene-derived C+-C-Se− 1,3-dipoles, reacted efficiently with methoxycarbonylallenes or dimethyl acetylenedicarboxylate to produce dihydroselenophenes or selenopheno[2,3-b]pyrazines, respectively, in high yields. Both reactions probably proceeded via a [3 + 2] cycloaddition of C+-C-Se− 1,3-dipoles with alkenes or alkyne followed by different transformations of the thiazole-spiro-selenophene intermediates. This work provides a concise and efficient strategy for the construction of multifunctional dihydroselenophenes and selenopheno[2,3-b]pyrazines, which are not easy accessible by other methods.

The unprecedented ring transformation from thiazoline-spiro-thiophene to thieno[2,3-b]pyrazine involved in the reaction of 2-thiocarbamoyl thiazolium salts with dimethyl acetylenedicarboxylate

Co-reporter:Yang Guang Ma and Ying Cheng

Chemical Communications 2007 (Issue 47) pp:5087-5089

Publication Date(Web):05 Oct 2007

DOI:10.1039/B712098B

Reaction of 2-thiocarbamoyl thiazolium salts with dimethyl acetylenedicarboxylate proceeded via a tandem [3 + 2] cycloaddition and a unprecedented ring transformation to produce functionalized thieno[2,3-b]pyrazine derivatives in good to excellent yields.

An unprecedented tandem 1,3-dipolar cycloaddition–cheletropic elimination: a facial approach to novel push–pull olefins

Co-reporter:Qing Zhu, Mei-Fang Liu, Bo Wang and Ying Cheng

Organic & Biomolecular Chemistry 2007 vol. 5(Issue 8) pp:1282-1286

Publication Date(Web):20 Mar 2007

DOI:10.1039/B701326D

The interaction of 2-(phenylthiocarbamoyl) imidazolium inner salts with dimethyl acetylenedicarboxylate produced dimethyl 2-(imidazolin-2-ylidene)-3-thioxobutanedioates in moderate to good yields. The process involved a tandem reaction comprising a 1,3-dipolar cycloaddition and an unprecedented cheletropic elimination of the phenyl isonitrile from a 2-phenyliminodihydrothiophene moiety. NMR and X-ray diffraction studies confirmed that the 2-(imidazolin-2-ylidene)-3-thioxobutanedioates are novel push–pull olefins and have potential applications in nonlinear optical materials.

Substrate-Controlled and Site-Selective [3+2] Cycloadditions of N-Heterocyclic Carbene Derived Ambident Dipoles

Co-reporter:Ying Cheng Dr.;Mei-Fang Liu;De-Cai Fang Dr.;Xue-Mei Lei

Chemistry - A European Journal 2007 Volume 13(Issue 15) pp:

Publication Date(Web):26 FEB 2007

DOI:10.1002/chem.200601482

2-Aryl thiocarbamoyl benzimidazolium and imidazolinium inner salts derived from benzimidazole and imidazoline carbenes are unique ambident C-C-S and C-C-N 1,3-dipolar systems, which undergo highly efficient and site-selective cycloaddition reactions with dimethyl acetylenedicarboxylate or dibenzoylacetylene to furnish spiro(imidazole-2,3′-thiophene) derivatives in excellent yields. When treated with ethyl propiolate, methyl acrylate or acrylonitrile, spiro(imidazole-2,3′-pyrrole) derivatives were formed in good yields. Theoretical studies revealed an asynchronous concerted mechanism for both the C-C-S and C-C-N 1,3-dipolar cycloaddition reactions. The site selectivity in the [3+2] cycloaddition reaction of ambident 1,3-dipoles was predictably regulated by both the electronic and steric effects of dipolarophiles.

A N-heterocyclic carbene derived highly regioselective ambident C–C–S and C–C–N 1,3-dipolar system

Co-reporter:Mei-Fang Liu, Bo Wang and Ying Cheng

Chemical Communications 2006 (Issue 11) pp:1215-1217

Publication Date(Web):01 Feb 2006

DOI:10.1039/B517700F

N-Heterocyclic carbene derived 2-phenylthiocarbamoyl benzimidazolium and imidazolinium inner salts are a unique ambident C–C–S and C–C–N 1,3-dipolar system able to undergo highly efficient and regioselective cycloaddition with dimethyl acetylenedicarboxylate and ethyl propiolate to furnish, respectively, spiro[imidazole-2,3′-thiophene] and spiro[imidazole-2,3′-pyrrole] derivatives in good to excellent yields.

A New Synthetic Approach to Carbamoylguanidinium Salts from N-Chloroguanidine and Aryl Isocyanates

Co-reporter:Cheng Ying;Gao Xing-Zhu;Shen Xiu-Min;Wang Jian

Chinese Journal of Chemistry 2005 Volume 23(Issue 4) pp:

Publication Date(Web):11 MAY 2005

DOI:10.1002/cjoc.200590448

A new synthetic method for the preparation of N-carbamoyl-N′,N′-disubstituted guanidinium salts was devel-oped from the nucleophilic reaction of N-chloroguanidines with aryl isocyanates.

The unprecedented ring transformation from thiazoline-spiro-thiophene to thieno[2,3-b]pyrazine involved in the reaction of 2-thiocarbamoyl thiazolium salts with dimethyl acetylenedicarboxylate

Co-reporter:Yang Guang Ma and Ying Cheng

Chemical Communications 2007(Issue 47) pp:NaN5089-5089

Publication Date(Web):2007/10/05

DOI:10.1039/B712098B

Reaction of 2-thiocarbamoyl thiazolium salts with dimethyl acetylenedicarboxylate proceeded via a tandem [3 + 2] cycloaddition and a unprecedented ring transformation to produce functionalized thieno[2,3-b]pyrazine derivatives in good to excellent yields.

Synthesis of novel synthetic intermediates from the reaction of benzimidazole and triazole carbenes with ketenimines and their application in the construction of spiro-pyrroles

Co-reporter:Jun-Ming Mo, Yang-Guang Ma and Ying Cheng

Organic & Biomolecular Chemistry 2009 - vol. 7(Issue 23) pp:NaN5019-5019

Publication Date(Web):2009/10/14

DOI:10.1039/B915215F

2-(2-Alkoxycarbonyl-1-arylamino-1-propenyl)benzimidazolium and 5-(2-alkoxycarbonyl-1-arylamino-1-propenyl)triazolium salts were synthesized in good yields from the reaction of benzimidazole and triazole carbenes with ketenimines. Upon treatment with a base, both salts were converted into novel 1,3-dipoles which underwent [3+2] cycloaddition reactions with electron-deficient alkynes and allenes to produce benzimidazole-spiro-pyrroles or triazole-spiro-pyrroles. This work provides novel synthons for the construction of multifunctional spiro-pyrrole derivatives that are not easy accessible by other synthetic methods and are potentially amenable to further transformations.

The reaction of β-lactam carbenes with 3,6-dipyridyltetrazines: switch of reaction pathways by 2-pyridyl and 4-pyridyl substituents of tetrazines

Co-reporter:Xiao-Rong Wang, Juan Xing, Cai-Xia Yan and Ying Cheng

Organic & Biomolecular Chemistry 2012 - vol. 10(Issue 5) pp:NaN977-977

Publication Date(Web):2011/10/26

DOI:10.1039/C1OB06595E

The reactions of β-lactam carbenes with both 3,6-di(2-pyridyl)tetrazine and 3,6-di(4-pyridyl)tetrazine were studied. It was found that β-lactam carbenes reacted with 3,6-di(2-pyridyl)tetrazine to produce 5-triazolo[1,5-a]pyridylpyrrol-2-ones in good yields, while with 3,6-di(4-pyridyl)tetrazine, they afforded pyrido[c]cyclopenta[b]pyrrol-2-ones in moderate yields. Both reactions were proposed to follow cascade mechanisms containing a 3,6a-dipyridylpyrrolo[3,2-c]pyrazol-5-one intermediate. The different pathways of the transformation of pyrrolo[3,2-c]pyrazol-5-ones were switched by the 2- and 4-pyridyl substituents. This work not only provided a simple and efficient strategy for the construction of novel triazolo[1,5-a]pyridine and pyrido[c]cyclopenta[b]pyrrole derivatives, respectively, but also revealed two different thermal transformation patterns of 3H-pyrazole compounds.

An unprecedented tandem 1,3-dipolar cycloaddition–cheletropic elimination: a facial approach to novel push–pull olefins

Co-reporter:Qing Zhu, Mei-Fang Liu, Bo Wang and Ying Cheng

Organic & Biomolecular Chemistry 2007 - vol. 5(Issue 8) pp:NaN1286-1286

Publication Date(Web):2007/03/20

DOI:10.1039/B701326D

The interaction of 2-(phenylthiocarbamoyl) imidazolium inner salts with dimethyl acetylenedicarboxylate produced dimethyl 2-(imidazolin-2-ylidene)-3-thioxobutanedioates in moderate to good yields. The process involved a tandem reaction comprising a 1,3-dipolar cycloaddition and an unprecedented cheletropic elimination of the phenyl isonitrile from a 2-phenyliminodihydrothiophene moiety. NMR and X-ray diffraction studies confirmed that the 2-(imidazolin-2-ylidene)-3-thioxobutanedioates are novel push–pull olefins and have potential applications in nonlinear optical materials.

The [3 + 2] cycloaddition reaction of thiazole carbene-derived C-C-Se 1,3-dipoles: a concise and highly efficient strategy for the construction of multifunctional dihydroselenophenes and selenopheno[2,3-b]pyrazines

Co-reporter:Jian-Hong Zhang and Ying Cheng

Organic & Biomolecular Chemistry 2009 - vol. 7(Issue 16) pp:NaN3270-3270

Publication Date(Web):2009/06/29

DOI:10.1039/B904575A

The first study on the reaction of C+-C-Se− 1,3-dipoles with electron-deficient alkenes and alkyne is reported. 2-Arylselenocarbamoylthiazolium inner salts, the unique thiazole carbene-derived C+-C-Se− 1,3-dipoles, reacted efficiently with methoxycarbonylallenes or dimethyl acetylenedicarboxylate to produce dihydroselenophenes or selenopheno[2,3-b]pyrazines, respectively, in high yields. Both reactions probably proceeded via a [3 + 2] cycloaddition of C+-C-Se− 1,3-dipoles with alkenes or alkyne followed by different transformations of the thiazole-spiro-selenophene intermediates. This work provides a concise and efficient strategy for the construction of multifunctional dihydroselenophenes and selenopheno[2,3-b]pyrazines, which are not easy accessible by other methods.

N-Heterocyclic carbene-catalyzed cascade reaction of 2-aroylvinylcinnamaldehydes with 2-aroylvinylchalcones: rapid assembly of six contiguous stereogenic centers with high diastereoselectivity

Co-reporter:Xing-Wen Fan and Ying Cheng

Organic & Biomolecular Chemistry 2014 - vol. 12(Issue 1) pp:NaN131-131

Publication Date(Web):2013/10/10

DOI:10.1039/C3OB41656A

N-Heterocyclic carbene-catalyzed reaction of 2-aroylvinylcinnamaldehydes with 2-aroylvinylchalcones proceeded via a triple Michael addition and intramolecular lactonization cascade to produce novel 9-(2-aroyl-3-aroylmethyl-1-indanyl)-3-arylindeno[2,1-c]pyran-1-ones in good yields with high diastereoselectivity. This reaction constructed six contiguous stereogenic centers in a single reactive event. Among 32 possible diastereoisomers that contain six stereocenters, only two diastereoisomers were detected with diastereomeric ratios being 10:1–28:1. This work opens up a new avenue for the synthesis of complex indane derivatives, a type of compound that has been reported to possess various biological and pharmaceutical activities.

The multicomponent reaction of imidazo[1,5-a]pyridine carbenes with phthalaldehydes and dimethyl acetylenedicarboxylate: a facile construction of benzo[d]furo[3,2-b]azepines

Co-reporter:Huan-Rui Pan, Xiao-Rong Wang, Cai-Xia Yan, Zhong-Xin Sun and Ying Cheng

Organic & Biomolecular Chemistry 2011 - vol. 9(Issue 7) pp:NaN2174-2174

Publication Date(Web):2010/12/16

DOI:10.1039/C0OB00746C

A study on the multicomponent reaction comprising both N-heterocyclic carbenes and substituted phthalaldehydes is reported. The imidazo[1,5-a]pyridine carbenes, namely imidazo[1,5-a]pyridine-3-ylidenes, reacted with phthalaldehydes and DMAD under very mild conditions to produce novel fused tricyclic benzo[d]furo[3,2-b]azepine derivatives. The resulting fused heterocyclic compounds are fluorescent and they give an emission around 500 nm with quantum yields (ΦF) being up to 0.81. This study provides not only a unique approach to fused azepine derivatives that are not easily accessible by other methods, but also opens a new avenue to complicated molecular skeletons. The fluorescence properties of long emission wavelength and high fluorescence quantum yields of some products predict their potential applications as optical sensors.

NHC Brønsted base-catalyzed transformations of isochromene derivatives: regulation of products by the structures of carbene catalysts

Co-reporter:Xing-Wen Fan and Ying Cheng

Organic & Biomolecular Chemistry 2012 - vol. 10(Issue 45) pp:NaN9084-9084

Publication Date(Web):2012/10/09

DOI:10.1039/C2OB26622A

Two different transformations of α-(isochromen-1-yl)ketones catalyzed by NHC Brønsted bases are reported. In the presence of a triazole carbene, α-(isochromen-1-yl)ketones isomerized into β-(2-(aroylmethylene)phenyl)-α,β-unsaturated ketones in 38–88% yields, while the same reaction catalyzed by an imidazole carbene produced 1-aroylnaphthalene derivatives in 90–99% yields. This work not only provides a new method for the synthesis of a novel type of α,β-unsaturated ketone and multi-substituted naphthalene derivatives, but also advances the application of NHC catalysts in the field of Brønsted base-catalysis.

N-Heterocyclic carbene-catalyzed cascade annulation reaction of o-vinylarylaldehydes with nitrosoarenes: one-step assembly of functionalized 2,3-benzoxazin-4-ones

Co-reporter:Zhong-Xin Sun and Ying Cheng

Organic & Biomolecular Chemistry 2012 - vol. 10(Issue 20) pp:NaN4094-4094

Publication Date(Web):2012/03/21

DOI:10.1039/C2OB25137J

The NHC-catalyzed reactions of ortho electron-deficient vinyl substituted arylaldehydes with nitrosoarenes were studied. The reactions produced multifunctional 2,3-benzoxazin-4-ones in good to excellent yields via a cascade aza-benzoin reaction between aldehyde and nitroso groups followed by an intramolecular oxo-Michael addition. The resulting 1-acetate substituted 2,3-benzoxazinones were transformed into a new type of β-hydroxycarboxylate derivatives or 3-oxo-1-isobenzofuranacetates, respectively, under different reductive conditions. This work not only provides a simple and efficient method for the construction of multifunctional 2,3-benzoxazin-4-ones of potential pharmacological interest, but also expands the application of NHC-catalyzed cascade reactions in the formation of carbon–heteroatom and heteroatom–heteroatom bonds.

Chiral N-heterocyclic carbene/Lewis acid cooperative catalysis of the reaction of 2-aroylvinylcinnamaldehydes: a switch of the reaction pathway by Lewis acid activation

Co-reporter:Zhan-Yong Wang, Ya-Li Ding, Gang Wang and Ying Cheng

Chemical Communications 2016 - vol. 52(Issue 4) pp:NaN791-791

Publication Date(Web):2015/11/06

DOI:10.1039/C5CC08866F

The chiral N-heterocyclic carbene/Lewis acid co-catalyzed reaction of 2-aroylvinylcinnamaldehydes produced good yields of indeno[1,2-c]furan-1-one derivatives with excellent enantioselectivity and diastereoselectivity. A switch of intramolecular cyclization to intermolecular dimerization was achieved by the cooperative catalysis of chiral triazole carbene and Ti(OPr-i)4 catalysts.

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Abstract