Prof. Baoguo Zhao

Professor Baoguo Zhao received his BSc in chemistry from Wuhan

University in 1996 and his MSc in organic chemistry under the

supervision of Professor Jianhua Xu from Nanjing University in 2002. He

obtained his PhD in organic chemistry under the supervision of Professor

Kuiling Ding at Shanghai Institute of Organic Chemistry, Chinese

Academy of Science, in 2006. He did postdoctoral research with Professor

Yian Shi at Colorado State University from 2006 to 2011. Since

September 2011, he has been appointed as a professor at the Chemistry Department of Shanghai

Normal University.

Address: 100 guiling Road, Room 8-217, Shanghai 200234, China

Email: zhaobg2006@shnu.edu.cn

Research Interests

A. Vitamin B6 based biomimetic asymmetric catalysis

Vitamin B6 family, i.e. pyridoxal 5’-phospate (PLP) and pyridoxamine 5′-phosphate, are one

of the most important coenzymes for many crucial biological transformations, such as

transamination, racemization of chiral amino acids, deamination, aldol condensation (threonine

synthesis), retro claisen cleavage, β-substitution (tryptophane synthesis), etc.. Although the vitamin

B6 has displayed versatile catalytic power in biological systems, its catalytic potential has not been

fully recognized in organic chemistry and awaits to be explored. Based on the unique structure of

vitamin B6, we design and synthesize chiral pyridoxals and pyridoxamines and imitate biological

processes for development of new biomimetic synthesis methodologies (Scheme 1). So far, we

have developed chiral pyridoxal/pyridoxamine catalyzed biomimetic asymmetric transamination

(Scheme 2) as well as biomimetic asymmetric carbonyl catalysis process (Schemes 3 and 4).

Scheme 1. Vitamin B6 based biomimetic catalysis

(a) Biomimetic asymmetric transamination

Transaminases are capable to catalyze the transformation of carbonyl compounds such as

-keto acids and unactivated ketones and aldehydes to the corresponding chiral amines. By using

chiral pyridoxals or pyridoxamines as the catalyst, we have developed biomimetic asymmetric

transamination of -keto acids, -ketoamides, and trifluromethyl ketones, respectively, to chiral

-amino acids, polypeptides, and trifluromethyl amines with excellent enantioselectivity and

mailto:zhaobg2006@shnu.edu.cn

stereoselectivity under very mild conditions. Our continuing studies include further development of

more efficient catalytic processes and expanding substrate scope.

Scheme 2. Biomimetic asymmetric transamination

(b) Biomimetic carbonyl catalysis

Enamine catalysis is a strategy to use chiral amines as catalysts to activate carbonyl groups for

α-functionalization (Scheme 3). As sharing the same imine intermediate, carbonyl catalysis is a

reverse strategy for activation of primary amines with carbonyl compounds as catalysts (Scheme 3).

By using N-quaternized pyridoxals as carbonyl catalysts, we have developed biomimetic carbonyl

catalysis process for -functionalization of primary amines without additional NH2 protecting

manipulations (Scheme 4). Our continuing studies will focus on exploring and expanding more

applications of carbonyl catalysis in organic synthesis.

Scheme 3. Carbonyl catalysis vs enamine catalysis

Scheme 4. Biomimetic carbonyl catalysis for asymmetric -functionalization of amines

B. Biomimetic Total Synthesis

We are interested in biomimetic total synthesis of natural products and related compounds

with high bioactivities. Bioactive properties will also be studied.

Publications

(43) Jianfeng Chen,1,2† Xing Gong,1† Jianyu Li,1 Yingkun Li,1 Jiguo Ma,1 Chengkang Hou,1

Guoqing Zhao,1 Weicheng Yuan,2* Baoguo Zhao1* “Carbonyl Catalysis Enables a

Biomimetic Asymmetric Mannich Reaction” Science 2018, in press.

(42) Tao Ding1, Yazhen Duan2, Hui Li2, Baoguo Zhao1*, Jun Yang2* “An Efficient HCl Promoted

Petasis Reaction of 2-Pyridinecarbaldehydes, Amines and 1,2-Oxborol-2(5H)-ols”

Tetrahedron Lett. 2018, 59, 2502.

(41) Chengkang Hou, Guoqing Zhao*, Dongfang Xu, Baoguo Zhao* “Enantioselective

Biomimetic Transamination of -Keto Acids Catalyzed by H4-Naphthalene-Derived Axially

Chiral Biaryl Pyridoxamines” Tetrahedron Lett. 2018, 59, 1028.

(40) Dongfang Xu, Baoguo Zhao* “Highly Regioselective Hydroformylation of Olefins with

Formic Acid Instead of Toxic and Flammable CO/H2” Sci. China Chem. 2017, 60, 839.

(39) Feng Liu, Jiaxin Tian, Yong Liu, Chuangan Tao, Hao Zhu, Aina Zhang, Dongfang Xu and

Baoguo Zhao* “Decarboxylative Umpolung of Conjugated Enal to β-Carbanion for

Intramolecular Nucleophilic Addition to Aldehyde” Org. Chem. Front. 2017, 4, 1586.

(38) Yong Ethan Liu, Zhaole Lu, Bo Li, Jiaxin Tian, Feng Liu, Junyu Zhao, Chengkang Hou,

Yingkun Li, Lili Niu, Baoguo Zhao* “Enzyme-Inspired Axially Chiral Pyridoxamines Armed

with a Cooperative Lateral Amine Chain for Enantioselective Biomimetic Transamination” J.

Am. Chem. Soc. 2016, 138, 10730.

(37) Xiaoyu Lan, Chuangan Tao, Xuliang Liu, Aina Zhang, Baoguo Zhao* “Asymmetric

Transamination of α-Keto Acids Catalyzed by Chiral Pyridoxamines” Org. Lett. 2016, 18,

3658.

(36) Jianfeng Chen, Junyu Zhao, Xing Gong, Dongfang Xu *, Baoguo Zhao * “A new type of

chiral-pyridoxamines for catalytic asymmetric transamination of -keto acids” Tetrahedron

Lett. 2016, 57, 4612.

(35) Limin Shi, Chuangan Tao, Qin Yang, Yong Ethan Liu, Jing Chen, Jianfeng Chen, Jiaxin Tian,

Feng Liu, Bo Li, Yongling Du, Baoguo Zhao* “Chiral Pyridoxal-Catalyzed Asymmetric

Biomimetic Transamination of α-Keto Acids” Org. Lett. 2015, 17, 5784.

(34) Bin Rong, Qin Yang, Hong Xu, Yifan Hu, Xuejing Cheng, Yong Liu, Baoguo Zhao*

“Pd-catalyzed Asymmetric α-Allylic Alkylation of Thioamides” Tetrahedron Lett. 2015, 56,

595.

(33) Juan Xu, Jing Chen, Lei Ding, Xuliang Liu, Dongfang Xu, Baoguo Zhao* “Synthesis of

α-Methylene-γ-amino acid Esters from Aldehydes via Aminative Umpolung Strategy” Adv.

Synth. Catal. 2014, 356, 3219.

(32) Xuliang Liu, Ang Gao, Lei Ding, Juan Xu, Dongfang Xu, Baoguo Zhao* “Aminative

Umpolung Synthesis of Vicinal Amines from Aromatic Aldehydes” Org. Lett. 2014, 16,

2118.

(31) Lei Ding, Jing Chen, Yifan Hu, Juan Xu, Xing Gong, Dongfang Xu, Baoguo Zhao*, Hexing

Li “Aminative Umpolung of Aldehydes to α-Amimo Anion Equivalents for Pd-catalyzed

Allyation: An Efficient Synthesis of Homoallylic Amines” Org. Lett. 2014, 16, 720.

(30) Bing Rong, Lei Ding, Hailei Yu, Qing Yang, Xuliang Liu, Dongfang Xu, Baoguo Zhao*

“Pd-Catalyzed Allylic Alkylation of Thioamides” Tetrahedron Lett. 2013, 54, 6501.

(29) Baoguo Zhao, Zhaobin Han, Kuiling Ding* “N-H Functions in Organometallic Catalysis”

Angew. Chem. Int. Ed. 2013, 52, 4744.

(28) Hailei Yu, Xuliang Liu, Lei Ding, Qin Yang, Bin Rong, Ang Gao, Baoguo Zhao*, Haifeng

Yang “Pd-Catalyzed α-Arylation of Thioamides” Tetrahedron Lett. 2013, 54, 3060.

(27) Richard G. Cornwall, Baoguo Zhao, Yian Shi* “Catalytic Asymmetric Synthesis of Cyclic

Sulfamides from Conjugated Dienes” Org. Lett. 2013, 15, 796.

(26) Yingguang Zhu, Baoguo Zhao, Yian Shi* “Highly Efficient Cu(I)-Catalyzed Oxidation of

Alcohols to Ketones and Aldehydes with Diaziridinone” Org. Lett. 2013, 15, 992.

(25) Thomas A. Ramirez, Baoguo Zhao and Yian Shi* “Recent advances in transition

metal-catalyzed sp3 C–H amination adjacent to double bonds and carbonyl groups” Chem.

Soc. Rev. 2012, 41, 931-942.

(24) Baoguo Zhao, Xingao Peng, Yingguang Zhu, Thamos A. Ramirez, Richard G. Cornwall,

Yian Shi* “Cu(I)-Catalyzed Diamination of Conjugated Dienes. Complementary

Regioselectivity from Two Distinct Mechanistic Pathways” J. Am. Chem. Soc. 2011, 133,

20890-20900.

(23) Xingao Peng, Yingguang Zhu, Thomas A. Ramirez, Baoguo Zhao, Yian Shi* “New

Reactivity of Oxaziridine: Pd(II)-Catalyzed Aromatic C-H Ethoxycarbonylation via C-C

Bond Cleavage” Org. Lett. 2011, 13, 5244-5247.

(22) Richard G. Cornwall, Baoguo Zhao, Yian Shi* “Complementary Regioselectivity in the

Cu(I)-Catalyzed Diamination of Conjugated Dienes To Form Cyclic Sulfamides” Org. Lett.

2011, 13, 434-437.

(21) Baoguo Zhao, Xingao Peng, Sunliang Cui, Yian Shi* “Cu(I)-catalyzed Regioselective

Diamination of Conjugated Dienes via Dual Mechanistic Pathways” J. Am. Chem. Soc. 2010,

132, 11009-11011.

(20) Baoguo Zhao, Haifeng Du, Sunliang Cui, Yian Shi* “Synthetic and Mechanistic Studies of

Pd(0)-Catalyzed Diamination of Conjugated Dienes” J. Am. Chem. Soc. 2010, 132,

3523-3532.

(19) Baoguo Zhao, Haifeng Du, Renzhong Fu, Yian Shi* “Pd(0)-Catalyzed Asymmetric Allylic

and Homoallylic Diamination of 4-Phenyl-1-butene with Di-tert-butyldiaziridinone” Org.

Synth. 2010, 87, 263.

(18) Thamos A. Ramirez, Baoguo Zhao, Yian Shi* “An effective C-C Double bond formation via

Cu(I)-Catalyzed dehydrogenation” Tetrahedron Lett. 2010, 51, 1822-1825.

(17) Baoguo Zhao, Haifeng Du, Yian Shi* “Cu(I)-catalyzed Diamination of Conjugated Olefins

with Tunable Counteranions. A Possible Approach to Asymmetric Diamination” J. Org.

http://pubs.acs.org/doi/abs/10.1021/ol303469a?prevSearch=%255BContrib%253A%2Bbaoguo%2Bzhao%255D&searchHistoryKey=http://pubs.acs.org/doi/abs/10.1021/ol303469a?prevSearch=%255BContrib%253A%2Bbaoguo%2Bzhao%255D&searchHistoryKey=http://pubs.acs.org/doi/abs/10.1021/ol303431h?prevSearch=%255BContrib%253A%2Bbaoguo%2Bzhao%255D&searchHistoryKey=http://pubs.acs.org/doi/abs/10.1021/ol303431h?prevSearch=%255BContrib%253A%2Bbaoguo%2Bzhao%255D&searchHistoryKey=http://pubs.rsc.org/en/content/articlelanding/2012/cs/c1cs15104ehttp://pubs.rsc.org/en/content/articlelanding/2012/cs/c1cs15104ehttp://pubs.rsc.org/en/journals/journal/cshttp://pubs.rsc.org/en/journals/journal/cshttp://pubs.acs.org/doi/abs/10.1021/ol102767j?prevSearch=%2528baoguo%2Bzhao%2529%2BNOT%2B%255Batype%253A%2Bad%255D%2BNOT%2B%255Batype%253A%2Bacs-toc%255D&searchHistoryKey=http://pubs.acs.org/doi/abs/10.1021/ol102767j?prevSearch=%2528baoguo%2Bzhao%2529%2BNOT%2B%255Batype%253A%2Bad%255D%2BNOT%2B%255Batype%253A%2Bacs-toc%255D&searchHistoryKey=

Chem. 2009, 74, 8392-8395.

(16) Baoguo Zhao, Haifeng Du, Yian Shi* “Cu(I)-Catalyzed C-H α-Amination of Aryl Ketones:

Direct Synthesis of Imidazolinones” J. Org. Chem. 2009, 74, 4411-4413.

(15) Yuehong Wen, Baoguo Zhao, Yian Shi* “Cu(I)-Catalyzed Diamination of Disubstituted

Terminal Olefins: An Approach to Potent NK1 Antagonist” Org. Lett. 2009, 11, 2365-2368.

(14) Rengzhong Fu, Baoguo Zhao, Yian Shi* “Synthesis of (+)-CP-99,994 via Pd(0)-Catalyzed

Asymmetric Allylic and Homoallylic C-H Diamination of Terminal Olefin” J. Org. Chem.

2009, 74, 7577-7580.

(13) Haifeng Du, Baoguo Zhao, Yian Shi* "Pd(0)-Catalyzed Diamination of

trans-1-Phenyl-1,3-butadiene with Di-tert-butyldiaziridinone as Nitrogen Source” Org. Synth.

2009, 86, 315.

(12) Baoguo Zhao, Haifeng Du, Yian Shi* “A Cu(I)-Catalyzed C-H α-Amination of Esters. Direct

Synthesis of Hydantoins” J. Am. Chem. Soc. 2008, 130, 7220-7221.

(11) Baoguo Zhao, Haifeng Du, Yian Shi* “Cu(I)-Catalyzed Cycloguanidination of Olefins” Org.

Lett, 2008, 10, 1087-1090.

(10) Haifeng Du, Baoguo Zhao, Yian Shi* “Catalytic Asymmetric Allylic and Homoallylic

Diamination of Terminal Olefins via Formal C-H Activation” J. Am. Chem. Soc. 2008, 130,

8590-8591.

(9) Haifeng Du, Baoguo Zhao, Weicheng Yuan, Yian Shi* “Cu(I)-Catalyzed Asymmetric

Diamination of Conjugated Dienes” Org. Lett. 2008, 10, 4231-4234.

(8) Baoguo Zhao, Xingao Peng, Zheng wang, Chungu Xia, Kuiling Ding* “Modular Chiral

Bidentate Phosphonites: Design, Synthesis, and Application in Catalytic Asymmetric

Hydroformylation Reactions” Chem. Eur. J. 2008, 14, 7847-7857.

(7) Baoguo Zhao, Weicheng Yuan, Haifeng Du, Yian Shi* “Cu(I)-Catalyzed Intermolecular

Diamination of Activated Terminal Olefins” Org. Lett. 2007, 9, 4943-4945.

(6) Haifeng Du, Baoguo Zhao, Yian Shi* “A Facile Pd(0)-Catalyzed Regio- and Stereoselective

Diamination of Conjugated Dienes and Trienes” J. Am. Chem. Soc. 2007, 129, 762-763.

(5) Haifeng Du, Weicheng Yuan, Baoguo Zhao, Yian Shi* “A Pd(0)-Catalyzed Diamination of

Terminal Olefins at Allylic and Homoallylic Carbons via Formal C-H Activation under

Solvent-Free Conditions” J. Am. Soc. Chem. 2007, 129, 7496-7497.

(4) Haifeng Du, Weicheng Yuan, Baoguo Zhao, Yian Shi* “Catalytic Asymmetric Diamination

of Conjugated Dienes and Triene” J. Am. Soc. Chem. 2007, 129, 11688-11689.

(3) Weicheng Yuan, Haifeng Du, Baoguo Zhao, Yian Shi* “A Mild Cu(I)-Catalyzed

Regioselective Diamination of Conjugated Dienes” Org. Lett. 2007, 9, 2589-2591.

(2) Baoguo Zhao, Zheng Wang, Kuiling Ding* “Practical by Ligand Design: A New Generation

of Monodentate Phosphoramidite Ligands for Rhodium Catalyzed Enantioselective

Hydrogenations” Adv. Synth. Catal. 2006, 348, 1049-1057

(1) Min Zhang, Huiying An, Baoguo Zhao, Jianhua Xu* “Aromatic annulation strategy for

naphthalenes fused at 1,2- and 3,4-positions with two heterocycles” Org. Biomol.

Chem. 2006, 4, 33-35.

Patents

(6) 赵宝国，刘勇,卢兆乐,李波，“一种手性联芳骨架吡哆胺类催化剂及其合成方

法与应用”， 申请号：201610444057.X。

(5) 赵宝国，陈剑锋,赵濬宇,龚幸，“一种新型手性开链吡哆胺催化剂及其合成方法与应

用”， 专利号：201610444112.5。

(4) 赵宝国，兰晓宇, 陶创安, 刘旭亮，“一种手性吡哆胺催化剂及其合成方法和应用”，

专利号：201610443128.4。

(3) 赵宝国，陈静，石力敏，刘勇，杨琴，陈剑锋，田家昕，陶创安，李波，许东芳“一

种新型吡哆素衍生物及其制备方法”，专利号：201510413900.3。

(2) 赵宝国，陈静，杨琴，陈剑锋，石力敏，刘勇（Yong Ethan Liu），龚幸，兰晓宇，

卢兆乐，刘勇 (Yong Liu)，陶创安，田家昕，许东芳，“一种吡哆醛催化剂及其合成

方法与应用”，专利号：201510415046.4。

(1) 赵宝国，陶创安，石力敏，刘勇，陈静，“一种手性吡哆醛催化剂及其合成方法与应

用”，专利号：201510427177.4。

Awards

(1) 入选上海市东方学者特聘教授，2010 年。

(2) 入选教育部“新世纪优秀人才计划”，2012 年。

(3) 入选上海市“浦江人才计划”，2012 年。

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