赵宝国
发布人:吴波  发布时间:2017-11-10   浏览次数:2669

赵宝国 (Baoguo Zhao)

赵宝国 (Dr. Baoguo Zhao) 博士,教授,有机化学专业。1996于武汉大学化学系获理学学士学位,2002年于南京大学化学系获理学硕士学位,2006中国科学院上海有机化学研究所理学博士学位,2006-2011年于美国科罗拉多州立大学化学系做博士后研究,2011年加入上海师范大学。

联系地址: 上海师范大学8号楼217室,上海市桂林路100 号,邮编:200234

Email: zhaobg2006@shnu.edu.cn


 

主要研究方向

1仿生不对称催化

在生物体内维生素B6,即吡哆醛/吡哆胺及其磷酸酯衍生物,是一类非常重要的辅酶,作为酶的反应中心,它能催化很多生物转化,尤其是生物体内胺类化合物的合成和转化,如:羰基转氨化合成手性胺、氨基酸的消旋化、胺的氧化(脱氨)、丝氨酸β-取代合成色氨酸、β-羟基氨基酸的逆aldol反应、和甘氨酸的aldol反应合成β-羟基-α-氨基酸等。尽管维生素B6在生物体系内发挥着强大的催化功能,负责催化各种胺的合成与转化,但它在有机合成中的催化性能和潜力却没有发挥出来,迄今为止还没有发展出基于Vitamin B6结构的有效催化体系,它在不对称催化中的应用更有待发展。我们研究的一个重要方向正是基于辅酶Vitamin B6的结构,设计和发展新型的手性吡哆醛/吡哆胺催化体系,仿生不对称催化多种化学转化 (Scheme 1)。基于这一思路,我们已经初步实现了手性吡哆醛/吡哆胺仿生催化转氨化反应 (Scheme 2),并且发展了以手性吡哆醛为催化剂的仿生羰基催化过程 (Scheme 3)

Scheme 1. 基于维生素B6的仿生催化



  1. 仿生不对称转氨

生物体内手性胺合成的一个重要途径是转氨酶催化羰基的不对称转氨化,它可以在非常温和的条件下实现由易得的羰基化合物一步合成手性胺。如酮酸转氨酶催化酮酸的不对称转氨化生成手性α-氨基酸,ω-转氨酶可以催化普通羰基如醛和非活化酮的转氨化生成相应的手性胺类化合物。我们用手性吡哆醛/吡哆胺模拟转氨酶,发展吡哆醛/吡哆胺仿生催化羰基不对称转氨化,合成各种重要的手性胺 (Scheme 2)

Scheme 2. 仿生不对称转氨化


  1. 仿生羰基催

烯胺催化,即胺催化羰基化合物(醛或酮)的-位的官能团化,是最重要的催化模式之一,在有机合成中有着非常广泛的应用 (Scheme 3)。与烯胺催化相反,羰基催化是用羰基化合物(醛或酮)来催化伯胺的α-官能团化,实现由简单的伯胺一步合成各种重要的、结构更加复杂的胺类化合物。该过程不需要对胺的NH2基团进行相应的上保护和去保护操作,合成步骤短、高效并且原子经济(Scheme 3)。但发展出合适的羰基催化剂并实现有效的羰基催化过程是有机化学中的一个难题,有待发展。受threonine aldolase催化氨基酸的aldol反应的启发,我们以N-甲基手性吡哆醛为羰基催化剂,催化伯胺α-位不对称官能团化 (Scheme 4)


Scheme 3. 羰基催化 vs 烯胺催化



Scheme 4. 仿生羰基催化不对称Mannich反应


2仿生全合成

基于天然产物的生物合成途径,合成高活性的天然产物及其类似物,并进行相关生物活性研究。


发表文章

(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/H2Sci. 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 groupsChem. 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-butyldiaziridinoneOrg. 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. 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 heterocyclesOrg. Biomol. Chem. 20064, 33-35.


申请专利

(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


荣誉与获奖

(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。

 


Zhaobaoguo Webpage in English.pdf