C H Bond Functionalization: New Strategies for the Synthesis of Complex Natural Products and Pharmaceuticals. Phil Knutson Ferreira Group 12/3/2015

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C H Bond Functionalization: New Strategies for the Synthesis of Complex Natural Products and Pharmaceuticals Phil Knutson Ferreira Group 12/3/2015

New strategies in organic synthesis nsf-cchf.com

What is C H Functionalization? D. Sames, et al. Science 2006, 312, 67-72.

What is C H Functionalization? D. Sames, et al. Science 2006, 312, 67-72.

What is not C H Functionalization? Friedel-Crafts acylation/alkylation Oxidative phenol-phenol coupling Allylic oxidation via SeO 2 or other stoichiometric transition metal Ortho- or remote-metalation via stoichiometric strong bases K. Itami, et al. Angew. Chem. Int. Ed. 2012, 51, 8960-9009.

Content Examples in complex molecule synthesis C-C Bond Formation Aromatic C H Arylation C(sp 2 ) H Alkenylation and Alkylation Pd-cat. Directed C(sp 3 ) H Functionalization C H Insertion of Metal Carbenoids C Heteroatom Bond Formation C H Amination (C H Insertion of Nitrenes) C H Amination (C H Insertion of Metal Nitrenoids) C H Allylic Oxidation C H Borylation C H Halogenation Two Total Syntheses Utilizing C H Functionalization

Types of C H Functionalization C-C Bond Formation Aromatic C H Arylation K. Fagnou, et al. J. Org. Chem. 2008, 73, 5022.

Aromatic C H Arylation D. Trauner, et al. Org. Lett. 2005, 7, 5207-5209.

Aromatic C H Arylation D. Trauner, et al. Org. Lett. 2005, 7, 5207-5209.

Types of C H Functionalization C-C Bond Formation Aromatic C H Arylation C(sp 2 ) H Alkenylation and Alkylation

C(sp 2 ) H Alkenylation and Alkylation R.G. Bergman, J.A. Ellman, et al. J. Am. Chem. Soc. 2005, 127, 13496-13497.

C(sp 2 ) H Alkenylation and Alkylation R.G. Bergman, J.A. Ellman, et al. J. Am. Chem. Soc. 2005, 127, 13496-13497.

C(sp 2 ) H Alkenylation and Alkylation R.G. Bergman, J.A. Ellman, et al. J. Am. Chem. Soc. 2005, 127, 13496-13497.

Types of C H Functionalization C-C Bond Formation Aromatic C H Arylation C(sp 2 ) H Alkenylation and Alkylation Directed C(sp 3 ) H Functionalization

Directed C(sp 3 ) H Functionalization D. Sames, et al. J. Am. Chem. Soc. 2002, 124, 11856-11857.

Types of C H Functionalization C-C Bond Formation Aromatic C H Arylation C(sp 2 ) H Alkenylation and Alkylation Directed C(sp 3 ) H Functionalization C H Insertion Metal Carbenoids

C H Insertion of Metal Carbenoids X. Lei, et al. J. Am. Chem. Soc. 2015, 137, 11946 11949.

Types of C H Functionalization C-C Bond Formation Aromatic C H Arylation C(sp 2 ) H Alkenylation and Alkylation Directed C(sp 3 ) H Functionalization C H Insertion of Metal Carbenoids C Heteroatom Bond Formation C H Amination (C H Insertion of Nitrenes)

C H Amination (Nitrene Insertion) H. Tokuyama, et al. Angew. Chem. Int. Ed. 2010, 49, 5925 5929.

Types of C H Functionalization C-C Bond Formation Aromatic C H Arylation C(sp 2 ) H Alkenylation and Alkylation Directed C(sp 3 ) H Functionalization C H Insertion of Metal Carbenoids C Heteroatom Bond Formation C H Amination (C H Insertion of Nitrenes) C H Amination (C H Insertion of Metal Nitrenoids)

C H Amination (C H Insertion of Metal Nitrenoids) J. Du Bois, et al. J. Am. Chem. Soc. 2003, 125, 11510-11511.

Types of C H Functionalization C-C Bond Formation Aromatic C H Arylation C(sp 2 ) H Alkenylation and Alkylation Directed C(sp 3 ) H Functionalization C H Insertion of Metal Carbenoids C Heteroatom Bond Formation C H Amination (C H Insertion of Nitrenes) C H Amination (C H Insertion of Metal Nitrenoids) C H Allylic Oxidation (Pd-Catalyzed) M. White, et al. J. Am. Chem. Soc., 2005, 127, 6970-6971. M. White, et al. Nature Chem. 2009, 125, 547-551.

C H Allylic Oxidation (Pd-Catalyzed) M. White, et al. Nature Chem. 2009, 125, 547-551.

C H Allylic Oxidation (Pd-Catalyzed) M. White, et al. Nature Chem. 2009, 125, 547-551.

C H Allylic Oxidation (Pd-Catalyzed) M. White, et al. Nature Chem. 2009, 125, 547-551.

C H Allylic Oxidation (Pd-Catalyzed) M. White, et al. Nature Chem. 2009, 125, 547-551.

Types of C H Functionalization C-C Bond Formation Aromatic C H Arylation C(sp 2 ) H Alkenylation and Alkylation Directed C(sp 3 ) H Functionalization C H Insertion of Metal Carbenoids C Heteroatom Bond Formation C H Amination (C H Insertion of Nitrenes) C H Amination (C H Insertion of Metal Nitrenoids) C H Allylic Oxidation (Pd-Catalyzed) C H Borylation

C H Borylation J. F. Hartwig, et al. J. Am. Chem. Soc. 2011, 133, 2088 2091.

Types of C H Functionalization C-C Bond Formation Aromatic C H Arylation C(sp 2 ) H Alkenylation and Alkylation Directed C(sp 3 ) H Functionalization C H Insertion of Metal Carbenoids C Heteroatom Bond Formation C H Amination (C H Insertion of Nitrenes) C H Amination (C H Insertion of Metal Nitrenoids) C H Allylic Amination/Oxidation (Pd-Catalyzed) C H Borylation C H Halogenation (Metal-Catalyzed)

C H Halogenation K. Itami, et al. Angew. Chem. Int. Ed. 2012, 51, 8960-9009.

Content Examples in complex molecule synthesis C-C Bond Formation Aromatic C H Arylation C(sp 2 ) H Alkenylation and Alkylation Pd-cat. Directed C(sp 3 ) H Functionalization C H Insertion of Metal Carbenoids C Heteroatom Bond Formation C H Amination (C H Insertion of Nitrenes) C H Amination (C H Insertion of Metal Nitrenoids) C H Allylic Oxidation C H Borylation C H Halogenation Two Total Syntheses Utilizing C H Functionalization

(+)-Austamide Y. Kishi, et al. J. Am. Chem. Soc. 1979, 101, 6786-6788. E. J. Corey, J. Am. Chem. Soc. 2002, 124, 7904-7905.

(+)-Austamide E. J. Corey, J. Am. Chem. Soc. 2002, 124, 7904-7905.

(+)-Austamide E. J. Corey, J. Am. Chem. Soc. 2002, 124, 7904-7905.

E. J. Corey, J. Am. Chem. Soc. 2002, 124, 7904-7905. (+)-Austamide

Dragmacidin D B. M. Stoltz, et al. J. Am. Chem. Soc. 2002, 124, 13179-13184. K. Itami, et al. J. Am. Chem. Soc. 2011, 133, 19660 19663.

Dragmacidin D K. Itami, et al. J. Am. Chem. Soc. 2011, 133, 19660 19663.

Dragmacidin D K. Itami, et al. J. Am. Chem. Soc. 2011, 133, 19660 19663.

Dragmacidin D K. Itami, et al. J. Am. Chem. Soc. 2011, 133, 19660 19663.

Dragmacidin D K. Itami, et al. J. Am. Chem. Soc. 2011, 133, 19660 19663.

K. Itami, et al. J. Am. Chem. Soc. 2011, 133, 19660 19663. Dragmacidin D

Comparing total syntheses K. Itami, et al. Angew. Chem. Int. Ed. 2012, 51, 8960-9009.

Summary Examples in complex molecule synthesis C-C Bond Formation Aromatic C H Arylation C(sp 2 ) H Alkenylation and Alkylation Pd-cat. Directed C(sp 3 ) H Functionalization C H Insertion of Metal Carbenoids C Heteroatom Bond Formation C H Amination (C H Insertion of Nitrenes) C H Amination (C H Insertion of Metal Nitrenoids) C H Allylic Oxidation C H Borylation C H Halogenation Two Total Syntheses Utilizing C H Functionalization

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