1、2019/2/20,1,答辩人：XXX 导师: XXX教授,光催化2-取代苯并噻唑的合成及芳烃C-H官能化研究New Synthetic Methods for the Preparation of 2-Substituted Benzothiazoles And Photocatalytic Direct C-H Arylation,2019/2/20,2,Contents1. Background 2. Research proposal 3. Work progress (I, II, III, IV) 4. Acknowledgment,2019/2/20,3,1.1. Backgro
2、und of Photoredox Chemistry,R: generic organic substituent FG: electron-withdrawing functional group,1. Background,Nicewicz, D. A.; MacMillan, D. W. C. Science 2008, 322, 77,Hedstrand, D. M.; Kellogg, R. M. Tetrahedron Lett. 1978, 19, 1255,2019/2/20,4,Dai, C.; Narayanam, J. M. R.; Stephenson, C. R.
3、J. Nat. Chem. 2011, 3, 140,Ischay, M. A.; Anzovino, M. E.; Du, J.; Yoon, T. P. J. Am. Chem. Soc. 2008, 31, 14604,2019/2/20,5,1.2. Background of 2-Substituted Benzothiazoles,Fatty acid amide hydrolase inhibitor,Antitumor agent,Zopolrestat,2019/2/20,6,1.2.1. Main Synthetic Methods of 2-Substituted Ben
4、zothiazoles,1.Bahrami, K. Khodaei, M. M. J. Org. Chem. 2008, 73, 6835 2.Yao. S.; Schafer-Hales, K. J.; Beleld, K. D. Org. Lett. 2007, 9, 5645 3.Bose, D. S.; Idrees, M. J. Org. Chem. 2006, 71, 8261 4.Joyce, L. L.; Evindar, G.; Batery, R. A. Chem. Commun. 2004, 446 5.Saha, P.; Ramana, T.; Ali, M. A.;
5、Paul, R.; Punniyamurthy,T. J. Org. Chem. 2009, 74, 8719 6.Inamoto, K.; Hasegawa, C.; Hiroya, K.; Doi, T. Org. Lett. 2008, 10, 5147 7.Joyce, L. L.; Batey, R. A. Org. Lett. 2009, 11, 2792 8.Mu, X.; Zou, J.; Tetrahedron Lett. 2005, 46, 4345,2019/2/20,7,Inamoto, K.; Hasegawa, C.; Hiroya, K.; Doi, T. Org
6、. Lett. 2008, 10, 5147,Joyce, L. L.; Batey, R. A. Org. Lett. 2009, 11, 2792,2019/2/20,8,2. Research proposal,?,2019/2/20,9,3.Work progress,I. Aerobic Visible-Light Photoredox Radical C-H Functionalization: Catalytic Synthesis of 2-Substituted Benzothiazoles,2019/2/20,10,a: HPLC yield ; b: Isolated y
7、ield; c: Under 5% O2 balloon.; d: 0.5 equiv DBU was used.e: Reaction was carried out in dark. f: Under air; g: Under 100% O2 balloon,Table 1. Optimization of Reaction Conditions,2019/2/20,11,Table 2. Synthesis of 2-Phenylbenzothiazoles,2019/2/20,12,Table 3. Substitutions on the 2-Phenyl group,2019/2
8、/20,13,Scheme 2 The Proposed Mechanism,Photoredox under sunlight,Scheme 1. Intramolecular Kinetic Study,2019/2/20,14,II. Heterogeneous Ligand-free Pd/C Catalyzed Synthesis of 2-Substituted Benzothiazoles,2019/2/20,15,Table 1. Optimization of Reaction Conditions,2019/2/20,16,Table 2. Synthesis of 2-A
9、rylbenzothiazoles,a: Reaction conditions: substrate (1 eq.), Pd/C (2 mol%), rt, N2 atmosphere, 24 hr. b: Isolated yield; c: Pd/C (5 mol%);,17,Table 3. Synthesis of2-Alkylbenzothiazoles,b: Isolated yield; c: Pd/C (5 mol%); d: Pd/C (10 mol%);,2019/2/20,18,III. Transition-Metal-Free Cyclization For the
10、 Preparation of 2-Substituted Benzothiazoles,2019/2/20,19,Table 1. Optimization of Reaction Conditions,2019/2/20,20,Table 2. Synthesis of 2-Arylbenzothiazoles,b: isolated yield , c: reaction time is 24h, d: reaction temperature was 120 C,2019/2/20,21,Table 3. Synthesis of 2-Alkylbenzothiazoles,b: is
11、olated yield, c: reaction temperature was 120 C,2019/2/20,22,4. Summary,1) visible-light is the reaction driving force 2) molecular oxygen is the terminal oxidant 3) C-H Functionalization,1) ligand-free 2) room temperature 3) can tolerate many functional groups,1) transition-metal-free 2) tolerate m
12、any functional groups 3) staring material readily available,IV: Visible-Light Photoredox in Homolytic Aromatic Substitution: Direct Arylation of Arenes with Aryl Halides,23,Sun, C. L.; Li, H.; Yu, D. G.; Yu, M.; Zhou, X.; Lu, X. Y.; Huang, K.; Zheng, S. F.; Li, B. J.; Shi, Z. J. Nat. Chem. 2010, 2,
13、1044,Liu, W.; Cao, H.; Zhang, H.; Chung, K. H.; He, C.; Wang, H.; Kwong, F. Y.; Lei, A. J. Am. Chem. Soc. 2010, 132, 16737,Shirakawa, E.; Itoh, K.; Higashino, T.; Hayashi, T. J. Am. Chem. Soc. 2010, 132, 15537,Liu, W.; Tian, F.; Wang, X.; Yu, H.; Bi, Y. Chem. Commun. 2013, 49, 2983,24,Nguyen, J. D.;
14、 DAmato, E. M.; Narayanam, J. M. R.; Stephenson, C. R. J. Nat. Chem. 2012, 4, 854,Kim, H.; Lee, C. Angew. Chem. Int. Ed. 2012, 51, 12303,25,碘苯的还原电位: -1.59-2.24V, -1.73v(Ir4+ Ir3+*) Versus SCE,Table 1. Optimization of Reaction Conditionsa,a: reaction conditions: iodobenzene (0.5 mmol), catalyst (0.5
15、mol%), base (3 equiv.) in benzene (3 mL), irradiated under a 14 W compact fluorescent lamp irradiation at room temperature. b: GC yield; c: freeze-thaw degassed; d: reaction was carried out in dark,26,Table 2. HAS reactions of aryl iodide with benzenea,27,Table 3HAS reactions of aryl bromide with be
16、nzenea,b: Isolated yield; c: the reaction temperature was at room temperature; d: the reaction temperature was at 35 C; e: the reaction temperature was 80 C; f: the reaction temperature was 90 C g: GC yield.,28,Table 4. HAS reactions of aryl halides with arenesa,29,Scheme 1. The Proposed Mechanism,3
17、0,2019/2/20,31,Budn, M. E.; Guastavino, J. F.; Rossi, R. A. Org. Lett. 2013, 15, 1174.,Our group,Org. Lett. 2013, 15, xxxx，DOI: 10.1021/ol400946k,2019/2/20,32,Publications:1. Aerobic Visible-Light Photoredox Radical Catalytic Synthesis of 2-Substituted BenzothiazolesYannan Cheng, Jun Yang, Yue Qu, a
18、nd Pixu Li* Org. Lett. 2012,14, 98101 Visible-Light Photoredox in Homolytic Aromatic Substitution: Direct Arylation of Arenes with Aryl Halides Yannan Cheng, Xiangyong Gu, and Pixu Li*Org. Lett. 2013, 15, xxxxxxxx Manuscripts in preparation: 2. Heterogeneous Ligand-free Pd/C Catalyzed Synthesis of 2
19、-Substituted Benzothiazoles3. Transition-Metal-Free Cyclization For the Preparation of 2-Substituted Benzothiazoles,2019/2/20,33,Acknowledgment:,本论文是在我的导师XXX教授的精心指导下完成的，该论文调研、选题、撰写到修订都凝结着李老师的很多心血。在研究生学习的三年时光里，李老师严谨的治学态度和科研思维都深深感染着我，同时指引我在科研工作中面对难关时要不抛弃，不放弃。他不仅亲自指导我的科研工作，同时还让我独立去探索新课题。他不单只对我们严格要求，还经常
20、鼓励我们，关心我们的日常生活，经常和我们打成一片去体育锻炼、郊游等休闲活动。所谓“学贵得师，亦贵得友”，李老师不仅是我的良师更是我的益友。深深感谢XXX教授在我研究生入学前对我的指导，使我在之后的研究生学习生活中更加得心应手。测试中心的老师给我的论文工作提供了大量的协助，在此对他们的辛勤劳动表示衷心的感谢。感谢材化部的领导、资料室、研究生处、图书馆的老师们所给予的诸多帮助。还要感谢陈XX、谷XX,XXX等师兄师姐们对我的扶持与帮助；感谢与我同时入学XXX的帮助与支持；感谢本课题组的XX、XX、XX最后感谢我的家人以及其他的亲朋好友对我学业的支持和帮助。,2019/2/20,34,Thanks for your attention !,
