1,4-Dilithio-1,3-dienes: reaction and synthetic applications

The development of organometallic reagents remains one of the most important frontiers in synthetic chemistry. Commonly used organometallic reagents (such as RLi and RMgBr) are typically monometallic compounds, although they aggregate in many cases. When two carbon-metal bonds are in the same molecule in close proximity, however, these two carbon-metal moieties may exhibit novel reactivity. In this Account, we outline our work on new reactions and synthetic applications of the organo-dilithio reagents 1,4-dilithio-1,3-butadienes. The 1,4-dilithio-1,3-butadienes can be accessed readily in high efficiency with a wide variety of substitution patterns on the butadienyl skeleton. The configuration has been predicted and demonstrated to favor a double dilithium bridging structure in both solution and solid states. The two Li atoms are bridged by a butadiene moiety and are in close proximity. By taking advantage of this unique configuration, we have developed useful and interesting synthetic methodologies. Three types of reactions of 1,4-dilithio-1,3-butadienes, termed dilithio reagents here, have been developed and are discussed. An intramolecular reaction is introduced in the first section. The reaction is a result of the intracooperative effect among the two C-Li moieties, the butadienyl bridge, and the substituents. A useful transformation from silylated 1,4-dilithio-1,3-butadienes to α-lithio siloles is described. Second, we discuss an intermolecular reaction that results from the intercooperative effect of the two C-Li moieties toward substrates. As an example of the formation of functionalized cyclic dianions from the linear dianions of the dilithio reagents and organic substrates, we describe the isolation and structural characterization of a novel type of cyclic dianion; that is, fully substituted oxy-cyclopentadienyl dilithium formed via the reaction of dilithio reagents with CO. We also describe diverse reactions of dilithio reagents with nitriles to form substituted pyridines, tricyclic 1-bipyrrolines, and siloles, demonstrating the remarkable effect of substituents on the butadienyl skeleton. Third, we discuss transmetalation of dilithio reagents to generate other organo-dimetallic compounds. This section focuses on organo-dicopper compounds and their reactivity toward the synthesis of strained ring systems, such as semibullvalenes and twisted four-membered rings, with the metal-mediated C-C bond-forming approach. In addition to these three representative reactions, other useful applications are also briefly introduced. The dimetallic 1,4-dilithio-1,3-butadienes and their transmetalated derivatives provide unique synthetic organometallic reagents that are very different from monometallic reagents, both in terms of reactivity and synthetic application. These organo-dimetallic reagents provide access to interesting and useful compounds that are not available by other means. Moreover, given the possibilities afforded, the study of organo-dimetallic and organo-polymetallic compounds should yield further synthetic applications in the near future.