Copper-Catalyzed Aerobic Oxidative C-H Functionalizations. Supervisor: Prof. Yong Huang Reporter: Weiyu Yin ( 殷韦玉 ) Date:

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1 Copper-Catalyzed Aerobic Oxidative C-H Functionalizations Supervisor: Prof. Yong Huang Reporter: Weiyu Yin ( 殷韦玉 ) Date:

2 Content Introduction C-H Oxidation Initiated by Single-Electron Transfer(SET) C-H Oxidation that Resemble Organometallic Reactions High-Valent Organometallic Copper Summary and Outlook Acknowledgement Main ref.: Stahl, Angew. Chem. Int. Ed. 2011, 50,

3 Introduction Selective Oxidation and Oxidative CH functionalization Oxidants: TBHP, Oxone, DDQ, IBX, O 2 O 2 Abundance, Low cost, Environmentally friendly byproduct(h 2 O), Potential industrial prospects wind Drawback: Poor selectivity Tolman, Nature, 2008, 455, Metalloenzyme intermediate 2

4 Introduction Selective Oxidation and Oxidative CH functionalization Oxidants: TBHP, Oxone, DDQ, IBX, O 2 O 2 Abundance, Low cost, Environmentally friendly byproduct(h 2 O), Potential industrial prospects wind High selectivity Tolman, Nature, 2008, 455, Metalloenzyme intermediate 3

5 Content Introduction C-H Oxidation Initiated by Single-Electron Transfer(SET) C-H Oxidation that Resemble Organometallic Reactions High-Valent Organometallic Copper Summary and Outlook Acknowledgement Main ref.: Stahl, Angew. Chem. Int. Ed. 2011, 50,

6 Homocouplings of naphthol derivative [1] Ha, Tetrahedron. 2004, 60, [2] Kozlowski, Org. Lett. 2001, 3, [3] Nakajima, J. Org. Chem. 1999, 64, [4] Nakajima, Tetrahedron Lett. 1995, 36,

7 Homocouplings of naphthol derivative Implicate a striking similarity between this synthetic catalyst system and certain biological copper oxidases, such as copper amine oxidases(caos) [1] Kozlowski, J. Org. Chem. 2003, 68, [2] Kozlowski, J. Am. Chem. Soc. 2008, 130,

8 Bromination and Clorination of Arenes [1] Gusevskaya, Chem. Commun. 2006, [2] Gusevskaya, Appl. Catal. A. 2006, 309, [3] Gusevskaya, Tetrahedron Lett. 2007, 48, [4] Stahl, Chem. Commun. 2009,

9 The bromination reaction turn red-brown in color upon heating Direct complexation of the arene to Cu(II) does not appear to be required for halogenation to proceed Stahl, Chem. Commun. 2009,

10 α-functionalization of Tertiary Amines Cross Dehydrogenative Coupling reaction Typical Oxidants: TBHP or DDQ 9 Klussmann, J. Am. Chem. Soc. 2011, 133,

11 α-functionalization of Tertiary Amines [1] Li, Green Chem. 2007, 9, [2] Li, Synlett. 2009, [3] Li, Chem. Commun. 2009, [4] Guo, Chem. Commun. 2009, [5] Zhang, J. Org. Chem. 2011, 76, [6] Miura, J. Org. Chem. 2011, 76,

12 Reactions of Amide-Enolates [1] Taylor, Org. Lett. 2010, 12, [2] Kündig, Angew. Chem. Int. Ed. 2009, 48, [2] Taylor, Chem. Commun. 2009,

13 Reactions of Amide-Enolates [1]Taylor, Org. Lett. 2010, 12, [2]Kündig, Angew. Chem. Int. Ed. 2009, 48, [2]Taylor, Chem. Commun. 2009,

14 Summary SET Electron-rich 13

15 Content Introduction C-H Oxidation Initiated by Single-Electron Transfer(SET) C-H Oxidation that Resemble Organometallic Reactions High-Valent Organometallic Copper Summary and Outlook Acknowledgement Main ref.: Stahl, Angew. Chem. Int. Ed. 2011, 50,

16 Chelate-Directed C-H Oxidation Reactions Yu, J. Am. Chem. Soc. 2006, 128,

17 Chelate-Directed C-H Oxidation Reactions Yu, J. Am. Chem. Soc. 2006, 128,

18 Oxidative Annulation Reactions [1] Buchwald, Angew. Chem. Int. Ed. 2008, 47, [2] Nagasawa, Angew. Chem. Int. Ed. 2008, 47,

19 [1] Nagasawa, J. Am. Chem. Soc. 2009, 131, [2] Bao, Adv. Synth. Catal. 2010, 352, [3] Zhu, J. Am. Chem. Soc. 2010, 132, [4] Punniyamurthy, Org. Lett. 2011,13, [5] Zhu, Angew. Chem. Int. Ed. 2011, 50,

20 [1] Nagasawa, J. Am. Chem. Soc. 2009, 131, [2] Bao, Adv. Synth. Catal. 2010, 352, [3] Zhu, J. Am. Chem. Soc. 2010, 132, [4] Punniyamurthy, Org. Lett. 2011,13, [5] Zhu, Angew. Chem. Int. Ed. 2011, 50,

21 [1] Nagasawa, J. Am. Chem. Soc. 2009, 131, [2] Bao, Adv. Synth. Catal. 2010, 352, [3] Zhu, J. Am. Chem. Soc. 2010, 132, [4] Punniyamurthy, Org. Lett. 2011,13, [5] Zhu, Angew. Chem. Int. Ed. 2011, 50,

22 Hetero-Functionalization of Terminal Alkynes Stahl, J. Am. Chem. Soc. 2008, 130,

23 Hetero-Functionalization of Terminal Alkynes Stahl, J. Am. Chem. Soc. 2008, 130,

24 Hetero-Functionalization of Terminal Alkynes [1] Stahl, J. Am. Chem. Soc. 2008, 130, [2] Jiao, J. Am. Chem. Soc. 2010, 132, [3] Han, J. Am. Chem. Soc. 2009, 131, [4] Qing, J. Am. Chem. Soc. 2010, 132,

25 Homo & Cross-Coupling Reactions of Arenes [1] Daugulis, J. Am. Chem. Soc. 2009, 131,

26 Homo & Cross-Coupling Reactions of Arenes [1] Daugulis, J. Am. Chem. Soc. 2009, 131, [2] Mori, Org. Lett. 2009, 11, [3] Hong, J. Am. Chem. Soc. 2010, 132,

27 Content Introduction C-H Oxidation Initiated by Single-Electron Transfer(SET) C-H Oxidation that Resemble Organometallic Reactions High-Valent Organometallic Copper Summary and Outlook Acknowledgement Main ref.: Stahl, Angew. Chem. Int. Ed. 2011, 50,

28 High-valent organometallic copper [1] Burton, J. Chem. Soc. Chem. Commun. 1989, [2] Osuka, J. Am. Chem. Soc. 2000, 122, [3] Stack, Angew. Chem. Int. Ed. 2002, 41, [4] Takui, Angew. Chem. Int. Ed. 2006, 45,

29 [1] Stahl, J. Am. Chem. Soc. 2008, 130, [2] Ribas, Chem. Sci. 2010, 1, [3] Stahl, J. Am. Chem. Soc. 2010, 132,

30 Summary and Outlook C-H Oxidation Initiated by Single-Electron Transfer(SET) C-H Oxidation that Resemble Organometallic Reactions High-Valent Organometallic Copper 29

31 Prof. Yong Huang All the Professors in SCBB All members in E203 Everyone here Acknowledgement 30

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48 Hetero-Functionalization of Terminal Alkynes and Electron Deficient Heteroarenes [3] Mori, Org. Lett. 2009, 11,

49 Summary 48