Iron-catalyzed Cross Coupling reactions From Rust to a .ppt

* Iron-catalyzed Cross Coupling reactions: From Rust to a Rising Star Weijun Liu Transition metal catalyzed cross couplings have seen incredible advances and applications, have wide scope and compatibility. But…..typically use palladium and nickel which are generally toxic and expensive. Expensive and/or sensitive ancillary ligands are required. Alkyl iodides, bromides and triflates are best. With special ligands alkyl chlorides may be used. Iron: A More Practical Alternative Iron is one of the most abundant metals on earth. (5.6% of earth’s crust. 4th most abundant element after oxygen, silicon, and aluminum. Nickel is 0.0084%, palladium is 0.0000015%, gold is 0.0000004% of Earth’s continental crust.) 2. Cheap ?PdCl2: $4005/150g $26.70/g ?NiCl2: $98.40/250g $0.39/g ?FeCl3: $30.40/1kg $0.03/g 3. nontoxic ?Prevalent in biological systems Content: Early Examples 2. Alkenyl Derivatives as Substrates 3. Aryl Derivatives as Substrates 4. Alkyl Derivatives as Substrates 5. O, N, S-Arylation 6. Oxidative Cross-coupling Early Examples J. Kochi, J. Am. Chem. Soc. 1971, 93, 1487 Kochi, J. J. Org. Chem. 1976, 41, 502 NMP as cosolvent Cahiez, G. Synthesis 1998, 1199 2. Alkenyl Derivatives as Substrates Cahiez, G. Synthesis 1998, 1199 Cahiez, G.; Knochel, P. Synlett 2001, 1901 60% 60% 3. Aryl Derivatives as Substrates Furster, A. Angew. Chem., Int. Ed. 2002, 41, 609 Proposed Formal Catalytic Cycle 4. Alkyl Derivatives as Substrates Furster, A. Angew. Chem., Int. Ed. 2004, 43, 3955 Furster, A. Angew. Chem., Int. Ed. 2004, 43, 3955 Furster, A. Angew. Chem., Int. Ed. 2004, 43, 3955 Only tertiary halides and alky chlorides were found be inert. Nakamura, E. J. Am. Chem. Soc. 2004, 126, 3686 Hayashi, T. Org. Lett. 2004, 6, 1279 Cossy, J. Angew. Chem., Int. Ed. 2007, 46, 6521 51% Chai, C.L.L. Adv. Synth., Catal. 2007, 349, 1015 5. O, N, S-Arylation Bolm, C. Angew. Chem., Int. Ed. 2007, 46, 8862 * * *