Chem 634 February 10, 2004References- Week 1 (corresponding authors in bold font) Prof. Fox1) Activation of Grignard Reagents: Lai, Y. H. Synthesis 1981, 585.2)Screttas, C. G.; Micha-Screttas, M. Hydrolithiation of .alpha.-olefins by a regiospecifictwo-step process. Transformation of alkyl phenyl sulfides to alkyllithium reagents. J.Org. Chem. 1978, 43, 1064-10713)Rottlander, M. B., L.; Cahiez, G.; Knochel, P. Stereoselective Preparation ofFunctionalized Alkenylmagnesium Reagents via an Iodine-Magnesium ExchangeReaction. J. Org. Chem. 1999, 1999, 1080-1081.4) ArI + iPrMgBr –––> ArMgBrBoymond, L.; Rottländer, M.; Cahiez, G.; Knochel, P. Preparation of HighlyFunctionalized Grignard Reagents by an Iodine-Magnesium Exchange Reaction and itsApplication in Solid-Phase Synthesis. Angew. Chem., Int. Ed. 1998, 37, 1701-1703.5) Directed Metallation: Snieckus, V. Directed ortho metalation. Tertiary amide andO-carbamate directors in synthetic strategies for polysubstituted aromatica. Chem. Rev.1990, 90, 879.6) Ph2CuLi x-ray structure: Nis Peter Lorenzen, Erwin Weiss. Synthesis andStructure of a Dimeric Lithium Diphenylcuprate: [{Li(OEt)2}(CuPh2)]2Angew. Chem. Int. Ed. 1990, 29, 3007) Synthesis of Cuprate reagents that bear functional groups:RZnI + CuCN•LiX –––> R[CuCN]ZnIKnochel, P.; Yeh, M. C. P.; Berk, S. C.; Talbert, J. Synthesis and reactivity toward acylchlorides and enones of the new highly functionalized copper reagents RCu(CN)ZnI. J.Org. Chem. 1988, 53, 2390-2392.General References to Cuprate Chemistry8) Lipshutz, B. H.; Sengupta, S. Organocopper reagents: Substitution, conjugateaddition, carbo/metallocupration, and other reactions. Org. React. (N.Y.) 1992, 41, 136.R SPhLiR LiI+ iPr2MgMg(iPr)9) Lipshutz, B. H. The Evolution of Higher Order Cyanocuprates. Synlett 1990, 119.10) Lipshutz, B. H.; Wilhelm, R. S. Chemistry of higher order, mixedorganocuprates.. The stereochemical outcome of substitution reactions at unactivatedsecondary centers using organocopper reagents. J. Am. Chem. Soc. 1982, 104, 4696-4698.IEt2CuLior Et2Cu(CN)Li2EtracemicBrEt(Me)CuLior Et2Cu(CN)Li2Et~100% inversion11) Chelation controlled SN2’PhODOPhNMe2CuLiPhDMe–• Gallina, C.; Ciattini, P. G. Conversion of allylic carbamates into olefins with lithiumdimethylcuprate. A new formal SN2' reaction. J. Am. Chem. Soc. 1979, 101, 1035-1036.• Goering, H. L.; Kantner, S. S.; Tseng, C. C. Alkylation of allylic derivatives. 4. On themechanism of alkylation of allylic N-phenylcarbamates with lithium dialkylcuprates. J.Org. Chem. 1983, 48, 715-721.12) SN2’ w/o chelateCH3ODOBuMgBrCH3DBuCH3H3CH3C10% CuCNTseng, C. C.; Paisley, S. D.; Goering, H. L. Alkylation of allylic derivatives. 11.Copper(I)-catalyzed cross coupling of allylic carboxylates with Grignard reagents. J.Org. Chem. 1986, 51, 2884-2891.13) For a discussion of the diaxial opening of cyclohexene oxide, see pp 526–531 of Elieland Wilen, Stereochemistry of Organic Compounds14) 1,4-addition of cyanocuprates to allylic epoxides•Marino, J. P.; Jaen, J. C. Stereospecific umpolung .alpha.' substitution of ketones viareactions of organocuprates with enol ethers of .alpha.,.beta.-epoxycyclohexanones. J.Am. Chem. Soc. 1982, 104, 3165-3172.•Marino, J. P.; Floyd, D. M. Tetrahedron Lett. 1979, 675•Wender, P. A.; Erhardt, J. M.; Letendre, L. J. Reaction of allylically substitutedenolates with organometallic reagents: a convenient source of enolonium ion equivalents.J. Am. Chem. Soc. 1981, 103, 2114-2116.15) Pd-catalyzed Cross coupling Reactions• Couplings of Aryl Chlorides-Littke, A. F.; Fu, G. C. Palladium-catalyzed coupling reactions of aryl chlorides. Angew.Chem., Int. Ed. Engl. 2002, 41, 4176-4211.• Heck Reaction- Whitcombe, N. J.; Hii, K. K.; Gibson, S. E. Advances in the Heck chemistry of arylbromides and chlorides. Tetrahedron 2001, 57, 7449-7476.- Heck, R. F. Palladium-Catalysed Vinylation of Organic Halides. Org. React. (N.Y.)1982, 27, 345.• Suzuki- Suzuki, A. Cross-coupling reactions via organoboranes. J. Organomet. Chem. 2002,653, 83-90.-Kotha, S.; Lahiri, K.; Kashinath, D. Recent applications of the Suzuki-Miyaura cross-coupling reaction in organic synthesis. Tetrahedron 2002, 58, 9633-9695.- Suzuki, A.; Brown, H. C. Organic Synthesis via Boranes, Vol 3. Aldrich/Milwaukee,WI, 2003• Stille-Farina, V.; Krishnamurthy, V.; Scott, W. J. The Stille Reaction. Org. React. (N.Y.)1997, 50, 1-652.- Kosugi, M.; Fugami, K. Overview of the Stille Protocol with Sn In Handbook ofOrganopalladium Chemistry for Organic Synthesis; Negishi, E.-i., de Meijere, A., Eds.;Wiley-Interscience, 2002; Vol. 1, pp 263-285.• Sonogashira Reaction -Sonogashira, K. Development of Pd-Cu catalyzed cross-coupling of terminal acetyleneswith sp2-carbon halides. J. Organomet. Chem. 2002, 653, 46-49.- Sonogashira, K. Cross-coupling reactions to sp carbon atoms. In Metal-CatalyzedCross-Coupling Reactions; Diederich, F., Stang, P. J., Eds.; Wiley-VCH, Inc: 605 ThirdAve/New York/NY 10158-0012, 1998, pp 203-229.- Axel Köllhofer, T. P., Herbert Plenio A Versatile Catalyst for the Sonogashira Couplingof Aryl Chlorides. Angew. Chem., Int. Ed. 2003, 42, 1056-1058.• Amination and C-O bond formation- Muci, A. R.; Buchwald, S. L. Cross-Coupling Reactions: Practical palladium catalystsfor C-N and C-O bond formation. Top. Curr. Chem. 2002, 219, 131-209.- Hartwig, J. F. Palladium-catalyzed amination of aryl halides and related reactions InHandbook of Organopalladium Chemistry for Organic Synthesis; Negishi, E.-i., deMeijere, A., Eds.; Wiley-Interscience, 2002; Vol. 1, pp 1051-1096.Ketone arylation-Fox, J. M.; Huang, X.; Chieffi, A.; Buchwald, S. L. Highly Active and SelectiveCatalysts for the Formation of -Aryl Ketones J. Am. Chem. Soc. 2000; 122(7); 1360-1370.16)R1ZnX + R2COCl + cat. Pd(0) –––> R1COR2Negishi, E-i. et al Palladium Catalyzed Acylation of Organozincs and otherOrganometallics as a Convenient Route to Ketone Tetrahedron Lett. 1983, 24, 518117)RBrR'BBNPd(OAc)2PCy3RR'Netherton, M. R.; Dai, C.; Neuschutz, K.; Fu, G. C. Room-Temperature Alkyl-AlkylSuzuki Cross-Coupling of Alkyl Bromides that Possess Hydrogens. J. Am. Chem. Soc.2001, 123, 10099-10100.18) Review of Collman’s Reagent: Na2Fe(CO)4Collman, J. P. Disodium Tetracarbonylferrate - a Transition Metal Analog of a GrignardReagent. Acc. Chem. Res. 1975, 8, 342.19) Cyanation of Arylhalides and aryldiazonium salts:- Review: Lindley, J. A. Copper Assisted Nucleophilic Substitution of Aryl