Xi-Sheng Wang

Novel and facile synthesis of 1-benzazepines via copper-catalyzed oxidative C(sp3)–H/C(sp2)–H cross-coupling

Co-reporter:Rui Wang;Ruo-Xing Jin;Zi-Yang Qin;Kang-Jie Bian

Chemical Communications 2017 vol. 53(Issue 90) pp:12229-12232

Publication Date(Web):2017/11/09

DOI:10.1039/C7CC07027F

A novel and facile synthetic strategy for the construction of 1-benzazepines has been developed via copper-catalyzed oxidative C(sp3)–H/C(sp2)–H cross-coupling directly from two inert C–H bonds. This transformation represents an atom- and step-economical way to synthesize biologically important seven-membered benzo-heterocycles compared with the known methods.

A Copper-Catalyzed Aerobic [1,3]-Nitrogen Shift through Nitrogen-Radical 4-exo-trig Cyclization

Co-reporter:Dr. Yan Li;Rui Wang;Tao Wang;Xiu-Fen Cheng;Xin Zhou;Fan Fei; Dr. Xi-Sheng Wang

Angewandte Chemie 2017 Volume 129(Issue 48) pp:15638-15642

Publication Date(Web):2017/11/27

DOI:10.1002/ange.201709894

AbstractA novel radical [1,3]-nitrogen shift catalyzed by copper diacetate under an oxygen atmosphere (1 atm) has been developed for the construction of a diverse range of indole derivatives from α,α-disubstituted benzylamine. In this reaction, oxygen was used as a clean terminal oxidant, and water was produced as the only by-product. Five inert bonds were cleaved, and two C−N bonds and one C−C double bond were constructed in one pot during this transformation. This unique method demonstrated broad application protential for the late-stage modification of biologically active natural products and drugs. Mechanistic investigations indicate that a unique 4-exo-trig cyclization of an aminyl radical onto a phenyl ring is involved in the catalytic cycle.

A Copper-Catalyzed Aerobic [1,3]-Nitrogen Shift through Nitrogen-Radical 4-exo-trig Cyclization

Co-reporter:Dr. Yan Li;Rui Wang;Tao Wang;Xiu-Fen Cheng;Xin Zhou;Fan Fei; Dr. Xi-Sheng Wang

Angewandte Chemie International Edition 2017 Volume 56(Issue 48) pp:15436-15440

Publication Date(Web):2017/11/27

DOI:10.1002/anie.201709894

AbstractA novel radical [1,3]-nitrogen shift catalyzed by copper diacetate under an oxygen atmosphere (1 atm) has been developed for the construction of a diverse range of indole derivatives from α,α-disubstituted benzylamine. In this reaction, oxygen was used as a clean terminal oxidant, and water was produced as the only by-product. Five inert bonds were cleaved, and two C−N bonds and one C−C double bond were constructed in one pot during this transformation. This unique method demonstrated broad application protential for the late-stage modification of biologically active natural products and drugs. Mechanistic investigations indicate that a unique 4-exo-trig cyclization of an aminyl radical onto a phenyl ring is involved in the catalytic cycle.

Copper-catalyzed oxidative C(sp3)–H/C(sp2)–H cross-coupling en route to carbocyclic rings

Co-reporter:Rui Wang;Yan Li;Ruo-Xing Jin

Chemical Science (2010-Present) 2017 vol. 8(Issue 5) pp:3838-3842

Publication Date(Web):2017/05/03

DOI:10.1039/C7SC00250E

Copper-catalyzed selective coupling of C(sp3)–H bonds with C(sp2)–H bonds has been developed. An aniline module was used as a directing group to generate an aminyl radical, which selectively cleaves the secondary and tertiary C(sp3)–H bonds via a 1,5-HAT process to forge six-membered carbocyclic rings.

Copper-Catalyzed Decarboxylative Atom Transfer Radical Addition of Iododifluoroacetate to Alkynyl Carboxylic Acids

Co-reporter:Gang Li, Yi-Xuan Cao, Chen-Guang Luo, Yi-Ming Su, Yan Li, Quan Lan, and Xi-Sheng Wang

Organic Letters 2016 Volume 18(Issue 19) pp:4806-4809

Publication Date(Web):September 12, 2016

DOI:10.1021/acs.orglett.6b02216

The first example of copper-catalyzed decarboxylative atom transfer radical addition of alkynyl carboxylic acids has been developed with a readily available fluoroalkyl halide. This novel protocol has demonstrated a unique difunctionalization of nonterminal alkynes with a broad substrate scope and excellent functional-group tolerance. Mechanistic investigations revealed that the catalytic cycle was initiated by the attack of a difluoroalkyl radical to an in situ generated alkynylcopper species.

Nickel-Catalyzed Monofluoroalkylation of Arylsilanes via Hiyama Cross-Coupling

Co-reporter:Yun Wu, Hao-Ran Zhang, Yi-Xuan Cao, Quan Lan, and Xi-Sheng Wang

Organic Letters 2016 Volume 18(Issue 21) pp:5564-5567

Publication Date(Web):October 17, 2016

DOI:10.1021/acs.orglett.6b02803

The first example of nickel-catalyzed monofluoroalkylation of arylsilanes has been developed with readily available fluoroalkyl halides. This novel transformation has demonstrated high reactivity, broad substrate scope, excellent functional group tolerance, and mild reaction conditions. The selective activation of a relatively inert C–Si bond for slow release of aryl carbanion is the key reason for reducing the amount of arylmetal species, which makes this method more promising for fluorine-containing modification of complex bioactive molecules. Mechanistic investigations indicate that a free fluoroalkyl radical is involved in this catalytic cycle.

Direct electrophilic trifluoromethylthiolation of N-benzyl indoles using AgSCF3

Co-reporter:Lan Ma, Xiu-Fen Cheng, Yan Li, Xi-Sheng Wang

Tetrahedron Letters 2016 Volume 57(27–28) pp:2972-2975

Publication Date(Web):6 July 2016

DOI:10.1016/j.tetlet.2016.05.086

•AgSCF3/I2/KI has been developed as a novel electrophilic trifluoromethylthiolating system.•Electrophilic trifluoromethylthiolation of N-benzylindoles has been developed.•Mechanistic studies indicate that ISCF3 generated in situ played as the active SCF3 reagent.A novel electrophilic trifluoromethylthiolation reaction system has been developed with AgSCF3 used directly as the SCF3 source, in the presence of KI/K2S2O8/I2. Various N-benzylindoles have been trifluoromethylthiolated successfully with this system, and the mechanism of investigation showed an electrophilic reagent was generated in situ.

Nickel-Catalyzed Decarboxylative Difluoroalkylation of ,-Unsaturated Carboxylic Acids

Co-reporter:Gang Li;Tao Wang;Fan Fei;Dr. Yi-Ming Su;Dr. Yan Li;Dr. Quan Lan;Dr. Xi-Sheng Wang

Angewandte Chemie International Edition 2016 Volume 55( Issue 10) pp:3491-3495

Publication Date(Web):

DOI:10.1002/anie.201511321

Abstract

The first example of nickel-catalyzed decarboxylative fluoroalkylation of α,β-unsaturated carboxylic acids has been developed with commonly available fluoroalkyl halides. This novel transformation has demonstrated broad substrate scope, excellent functional-group tolerance, mild reaction conditions, and excellent stereoselectivity. Mechanistic investigations indicate that a fluoroalkyl radical is involved in the catalytic cycle.

Nickel-Catalyzed Decarboxylative Difluoroalkylation of ,-Unsaturated Carboxylic Acids

Co-reporter:Gang Li;Tao Wang;Fan Fei;Dr. Yi-Ming Su;Dr. Yan Li;Dr. Quan Lan;Dr. Xi-Sheng Wang

Angewandte Chemie 2016 Volume 128( Issue 10) pp:3552-3556

Publication Date(Web):

DOI:10.1002/ange.201511321

Abstract

The first example of nickel-catalyzed decarboxylative fluoroalkylation of α,β-unsaturated carboxylic acids has been developed with commonly available fluoroalkyl halides. This novel transformation has demonstrated broad substrate scope, excellent functional-group tolerance, mild reaction conditions, and excellent stereoselectivity. Mechanistic investigations indicate that a fluoroalkyl radical is involved in the catalytic cycle.

Pd-Catalyzed C(sp3)–H Carbonylation of Alkylamines: A Powerful Route to γ-Lactams and γ-Amino Acids

Co-reporter:Pei-Long Wang, Yan Li, Yun Wu, Chao Li, Quan Lan, and Xi-Sheng Wang

Organic Letters 2015 Volume 17(Issue 15) pp:3698-3701

Publication Date(Web):July 16, 2015

DOI:10.1021/acs.orglett.5b01658

A novel Pd-catalyzed direct C(sp3)–H carbonylation of alkylamines for the synthesis of γ-lactams and γ-amino acids has been developed, in which TEMPO was used as the crucial sole oxidant. The synthetic prospect was demonstrated by the concise total synthesis of rac-Pregbalin.

Pd(II)-catalyzed, controllable C–H mono-/diarylation of aryl tetrazoles: concise synthesis of Losartan

Co-reporter:Yan-Jun Ding, Yan Li, Sheng-Yu Dai, Quan Lan and Xi-Sheng Wang

Organic & Biomolecular Chemistry 2015 vol. 13(Issue 11) pp:3198-3201

Publication Date(Web):20 Jan 2015

DOI:10.1039/C4OB02453B

A palladium(II)-catalyzed C–H arylation directed by tetrazole, a metabolically stable surrogate for the carboxylic acid group in drug design, has been developed. Excellent mono-/di-selectivity was achieved through adjustment of the protecting site on the tetrazole ring. The synthetic utility of this new transformation was demonstrated in the concise total synthesis of Losartan.

Pd(II)-catalyzed C–H arylation of aryl and benzyl Weinreb amides

Co-reporter:Yan Wang, Kai Zhou, Quan Lan and Xi-Sheng Wang

Organic & Biomolecular Chemistry 2015 vol. 13(Issue 2) pp:353-356

Publication Date(Web):24 Oct 2014

DOI:10.1039/C4OB02039A

The first example of palladium-catalyzed ortho-C–H arylation of aryl and benzyl Weinreb amides was developed, in which HOTf was used as a key promoter. This method exhibits good functional group tolerance, a broad substrate scope of both Weinreb amides and aryl iodides, high mono-selectivity and mild reaction conditions.

Nickel-Catalyzed Monofluoromethylation of Aryl Boronic Acids

Co-reporter:Yi-Ming Su;Guang-Shou Feng;Zhen-Yu Wang;Dr. Quan Lan ;Dr. Xi-Sheng Wang

Angewandte Chemie 2015 Volume 127( Issue 20) pp:6101-6105

Publication Date(Web):

DOI:10.1002/ange.201412026

Nickel-Catalyzed Monofluoromethylation of Aryl Boronic Acids

Co-reporter:Yi-Ming Su;Guang-Shou Feng;Zhen-Yu Wang;Dr. Quan Lan ;Dr. Xi-Sheng Wang

Angewandte Chemie International Edition 2015 Volume 54( Issue 20) pp:6003-6007

Publication Date(Web):

DOI:10.1002/anie.201412026

Visible Light-Mediated C–H Difluoromethylation of Electron-Rich Heteroarenes

Co-reporter:Yi-Ming Su, Yu Hou, Feng Yin, Yue-Ming Xu, Yan Li, Xiaoqi Zheng, and Xi-Sheng Wang

Organic Letters 2014 Volume 16(Issue 11) pp:2958-2961

Publication Date(Web):May 9, 2014

DOI:10.1021/ol501094z

A novel method for visible-light photoredox-catalyzed difluoromethylation of electron-rich N-, O-, and S-containingheteroarenes under mild reaction conditions is developed. Mechanistic investigation indicates that the net C–H difluoromethylation proceeds through an electrophilic radical-type pathway.

Silver-Mediated Radical Aryltrifluoromethylthiolaton of Activated Alkenes

Co-reporter:Feng Yin and Xi-Sheng Wang

Organic Letters 2014 Volume 16(Issue 4) pp:1128-1131

Publication Date(Web):February 5, 2014

DOI:10.1021/ol403739w

The first example of silver-mediated oxidative aryltrifluoromethylthiolation of activated alkenes to produce valuable trifluoromethylthiole-containing oxindoles was developed. Mechanistic investigations indicated that this novel transformation proceeded through a unique F3CS• radical addition path, thus providing a practical and easy-handling method to generate a F3CS• radical in the laboratory.

Pd(0)-Catalyzed radical aryldifluoromethylation of activated alkenes

Co-reporter:Jian-Yong Wang, Yi-Ming Su, Feng Yin, Yan Bao, Xin Zhang, Yue-Ming Xu and Xi-Sheng Wang

Chemical Communications 2014 vol. 50(Issue 31) pp:4108-4111

Publication Date(Web):27 Feb 2014

DOI:10.1039/C3CC49315F

A Pd(0)-catalyzed intramolecular aryldifluoromethylation of activated alkenes under mild reaction conditions has been developed. This reaction provides a new method for construction of a variety of difluoromethylated oxindoles. Mechanistic investigations indicate that a difluoromethyl radical, which was triggered by Pd(0), initiated the cascade sequence through an addition to the alkene.

Palladium-Catalyzed CF Bond Formation via Directed CH Activation

Co-reporter:Yan Li;Yun Wu;Guang-Shui Li

Advanced Synthesis & Catalysis 2014 Volume 356( Issue 7) pp:1412-1418

Publication Date(Web):

DOI:10.1002/adsc.201400101

Iron-catalyzed radical aryldifluoromethylation of activated alkenes to difluoromethylated oxindoles

Co-reporter:Jian-Yong Wang, Xin Zhang, Yan Bao, Yue-Ming Xu, Xiu-Fen Cheng and Xi-Sheng Wang

Organic & Biomolecular Chemistry 2014 vol. 12(Issue 30) pp:5582-5585

Publication Date(Web):03 Jun 2014

DOI:10.1039/C4OB00758A

An iron-catalyzed aryldifluoromethylation of activated alkenes under mild reaction conditions has been developed, which is a rare example where a cosolvent is used to improve the reaction yield along with Fenton's reagent and thus provides an economic and green method for the synthesis of a variety of difluoromethylated oxindoles. Preliminary mechanistic investigations indicate a radical addition path.

Pd(II)-Catalyzed Enantioselective C–H Activation/C–O Bond Formation: Synthesis of Chiral Benzofuranones

Co-reporter:Xiu-Fen Cheng ; Yan Li ; Yi-Ming Su ; Feng Yin ; Jian-Yong Wang ; Jie Sheng ; Harit U. Vora ; Xi-Sheng Wang ;Jin-Quan Yu

Journal of the American Chemical Society 2013 Volume 135(Issue 4) pp:1236-1239

Publication Date(Web):January 10, 2013

DOI:10.1021/ja311259x

Pd(II)-catalyzed enantioselective C–H activation of phenylacetic acids followed by an intramolecular C–O bond formation afforded chiral benzofuranones. This reaction provides the first example of enantioselecctive C–H functionalizations through Pd(II)/Pd(IV) redox catalysis.

Pd-Catalyzed C–H Lactonization for Expedient Synthesis of Biaryl Lactones and Total Synthesis of Cannabinol

Co-reporter:Yan Li, Yan-Jun Ding, Jian-Yong Wang, Yi-Ming Su, and Xi-Sheng Wang

Organic Letters 2013 Volume 15(Issue 11) pp:2574-2577

Publication Date(Web):May 10, 2013

DOI:10.1021/ol400877q

A practical Pd(II)/Pd(IV)-catalyzed carboxyl-directed C–H activation/C–O cyclization to construct biaryl lactones has been developed. The synthetic utility of this new reaction was demonstrated in an atom-economical and operationally convenient total synthesis of the natural product cannabinol from commercially available starting materials, with the newly developed method used for two key steps.

Rhodium-Catalyzed CH Olefination of Aryl Weinreb Amides

Co-reporter:Yan Wang;Chao Li;Yan Li;Feng Yin

Advanced Synthesis & Catalysis 2013 Volume 355( Issue 9) pp:1724-1728

Publication Date(Web):

DOI:10.1002/adsc.201300174

Abstract

A rhodium(III)-catalyzed oxidative CH olefination directed by Weinreb amides, a class of well developed versatile building blocks in organic synthesis, has been developed with air as the terminal oxidant. The reactions proceed with excellent reactivity, good functional group tolerance and high yields.

Pd(0)-Catalyzed radical aryldifluoromethylation of activated alkenes

Co-reporter:Jian-Yong Wang, Yi-Ming Su, Feng Yin, Yan Bao, Xin Zhang, Yue-Ming Xu and Xi-Sheng Wang

Chemical Communications 2014 - vol. 50(Issue 31) pp:NaN4111-4111

Publication Date(Web):2014/02/27

DOI:10.1039/C3CC49315F

A Pd(0)-catalyzed intramolecular aryldifluoromethylation of activated alkenes under mild reaction conditions has been developed. This reaction provides a new method for construction of a variety of difluoromethylated oxindoles. Mechanistic investigations indicate that a difluoromethyl radical, which was triggered by Pd(0), initiated the cascade sequence through an addition to the alkene.

Pd(II)-catalyzed, controllable C–H mono-/diarylation of aryl tetrazoles: concise synthesis of Losartan

Co-reporter:Yan-Jun Ding, Yan Li, Sheng-Yu Dai, Quan Lan and Xi-Sheng Wang

Organic & Biomolecular Chemistry 2015 - vol. 13(Issue 11) pp:NaN3201-3201

Publication Date(Web):2015/01/20

DOI:10.1039/C4OB02453B

A palladium(II)-catalyzed C–H arylation directed by tetrazole, a metabolically stable surrogate for the carboxylic acid group in drug design, has been developed. Excellent mono-/di-selectivity was achieved through adjustment of the protecting site on the tetrazole ring. The synthetic utility of this new transformation was demonstrated in the concise total synthesis of Losartan.

Iron-catalyzed radical aryldifluoromethylation of activated alkenes to difluoromethylated oxindoles

Co-reporter:Jian-Yong Wang, Xin Zhang, Yan Bao, Yue-Ming Xu, Xiu-Fen Cheng and Xi-Sheng Wang

Organic & Biomolecular Chemistry 2014 - vol. 12(Issue 30) pp:NaN5585-5585

Publication Date(Web):2014/06/03

DOI:10.1039/C4OB00758A

An iron-catalyzed aryldifluoromethylation of activated alkenes under mild reaction conditions has been developed, which is a rare example where a cosolvent is used to improve the reaction yield along with Fenton's reagent and thus provides an economic and green method for the synthesis of a variety of difluoromethylated oxindoles. Preliminary mechanistic investigations indicate a radical addition path.

Copper-catalyzed oxidative C(sp3)–H/C(sp2)–H cross-coupling en route to carbocyclic rings

Co-reporter:Rui Wang, Yan Li, Ruo-Xing Jin and Xi-Sheng Wang

Chemical Science (2010-Present) 2017 - vol. 8(Issue 5) pp:NaN3842-3842

Publication Date(Web):2017/03/15

DOI:10.1039/C7SC00250E

Copper-catalyzed selective coupling of C(sp3)–H bonds with C(sp2)–H bonds has been developed. An aniline module was used as a directing group to generate an aminyl radical, which selectively cleaves the secondary and tertiary C(sp3)–H bonds via a 1,5-HAT process to forge six-membered carbocyclic rings.

Pd(II)-catalyzed C–H arylation of aryl and benzyl Weinreb amides

Co-reporter:Yan Wang, Kai Zhou, Quan Lan and Xi-Sheng Wang

Organic & Biomolecular Chemistry 2015 - vol. 13(Issue 2) pp:NaN356-356

Publication Date(Web):2014/10/24

DOI:10.1039/C4OB02039A

The first example of palladium-catalyzed ortho-C–H arylation of aryl and benzyl Weinreb amides was developed, in which HOTf was used as a key promoter. This method exhibits good functional group tolerance, a broad substrate scope of both Weinreb amides and aryl iodides, high mono-selectivity and mild reaction conditions.

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