AbstractThe addition of carbanionic organometallic compounds (usually RLi or RMgX) to a carbonyl group—a key step in numerous syntheses—is not always straightforward. Depending on the substrate, various complications and problems may arise, but in many cases these can be remedied by addition of (RO)3TiCl, (RO)3ZrCl or (R2N)3TiX to the classic lithium and Grignard reagents. This usually leads to formation of stable organo‐titanium and ‐zirconium compounds which react highly selectively with carbonyl groups. For example, CH3Ti(OiPr)3reacts five orders of magnitude faster with benzaldehyde than with acetophenone at room temperature; reagents of the type RTi(OiPr)3add smoothly to nitro‐, ido‐, or cyano‐subsituted benzaldehyde, and the reactions may be performed in chlorinated solvents or acetonitrile; the zirconium analogues have particularly low basicity and add in high yield to α‐ and β‐tetralones or to substrates containing a nitroaldol group; the inclusion of chiral OR*groups gives enantioselective reagents (up to 90%ee); allylic (RO3)Ti‐ derivatives react only at the more highly substituted carbon atom and, in addition, react diastereoselectively (up to 98%ds) with unsymmetrical ketones. Finally, titanium reagents have also been found to effect novel transformations such as direct geminal dialkylation (CO→CMe2) and alkylative amination [CO→CR(NR 2′)]. The modification and finetuning (“taming”) of carbonyl reactivity obtainable by use of the new reagents is not dearly bought; starting materials are the cheap and harmless “titanates”, “zirco