Cross-coupling reactions cyclopropane

Negishi E, Tan Z (2005) Diastereoselective, Enantioselective, and Regioselective Carbo-alumination Reactions Catalyzed by Zirconocene Derivatives. 8 139-176 Netherton M, Fu GC (2005)Pa]ladium-catalyzed Cross-Coupling Reactions of Unactivated Alkyl Electrophiles with Organometallic Compounds. 14 85-108 Nicolaou KC, King NP, He Y (1998) Ring-Closing Metathesis in the Synthesis of EpothUones and Polyether Natmal Products. 1 73-104 Nishiyama H (2004) Cyclopropanation with Ruthenium Catalysts. 11 81-92 Noels A, Demonceau A, Delaude L (2004) Ruthenium Promoted Catalysed Radical Processes toward Fine Chemistry. 11 155-171... 

Treatment of gem-dibromocyclopropane 34 with Bu3ZnLi from —85 to 0°C generates 1-butylcyclopropylzinc 36 via the 1,2-migration of the zincate carbenoid 35 (equation 27)24. Subsequent Pd°-catalyzed cross-coupling reactions afford cyclopropane... 

The cyclopropyl effect has controlled the regioselectivity of the cross-coupling reactions of propargylic/allenylic metallic species with electrophiles afford alkynic cyclopropanes (Scheme 9).70 Cyclopropyl ring strain, which makes the formation of vinylidenecyclopropanes unfavourable, is believed to control the regioselectivity. 

Alkenylboron compounds cyclopropanations, 9, 181 haloetherification, 9, 182 hydrogenation and epoxidation, 9, 182 metal-catalyzed reactions, 9, 183 metallic reagent additions, 9, 182 via radical addition reactions, 9, 183 5-Alkenylboron compounds, cross-coupling reactions, 9, 208 Alkenyl complexes with cobalt, 7, 51 with copper, 2, 160, 2, 174 with Cp Re(CO) (alkene)3 , 5, 915-916 with dicarbonyl(cyclopentadienyl)hydridoirons, 6, 175 with gold, 2, 255... 

In a detailed investigation of the mechanism and scope of palladium catalyzed amination of five-membered heterocycles, the 1-methyl-3-bromoindole 145 was aminated with secondary amines to the 3-aminoindoles 146. Similar results were obtained for l-methyl-2-bromoindole <03JOC2861>. Rhodium-catalyzed cyclopropanation reactions involving 1-methyl-3-diazooxindole and exocyclic alkenes provided novel dispirocyclic cyclopropanes <03SL1599>. New applications of palladium-mediated cross-coupling reactions have been utilized to prepare a variety of functionalized indoles. Suzuki-Miyaura coupling reactions of indole-3-boronates <03H(59)473> and indole-5-boronates <03H(60)865> were utilized to prepare inhibitors of lipid peroxidation and melatonin analogues, respectively. 

The ring expansion of oxyglycal-derived gm-dihalo 1,2-cyclopropanate oxyglycals provides stable seven-membered halo-oxepines, that are thus suitable precursors for further functionalizations. In a study, vinyl bromide of the bromo-oxepine was used for the metal-catalyzed cross-coupling reactions, namely, Heck, Suzuki, and Sonogashira reactions, so as to generate 2-deoxy-2-C-alkyl/ary/alkynyl septanosides [33]. 

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