Functionalization of heterocyclic compounds using polyfunctional magnesium and zinc reagents

Abstract

SummaryIn this review we summarize the most important procedures for the preparation of functionalized organzinc and organomagnesium reagents. In addition, new methods for the preparation of polyfunctional aryl- and heteroaryl zinc- and magnesium compounds, as well as new Pd-catalyzed cross-coupling reactions, are reported herein. Experimental details are given for the most important reactions in the Supporting Information File 1 of this article.

Suzuki-Miyaura Cross-Coupling of Unprotected, Nitrogen-Rich Heterocycles: Substrate Scope and Mechanistic Investigation

“…4 Instead, such molecules are obtained either via construction of the heterocyclic rings with the desired residues already attached, 5 or via functionalization using the corresponding N -protected analogues. 6 While these routes have merit, they are often limited in substrate scope and/or necessarily require extra protection/deprotection steps. Thus, access to facile methods for the direct use of these acidic, nitrogen-rich heterocycles in palladium-catalyzed C-C cross-coupling processes is highly desirable.…”

Nickel‐Catalyzed Csp2Csp3 Bond Formation by CarbonFluorine Activation

“…The zinc reagents are significantly less reactive towards functional groups than many other organometallic reagents and therefore offer high synthetic utility. [10] In addition to the limited number of diorganozinc reagents that are commercially available, many organozinc halides can be either purchased or synthesized by using well-established protocols. [11] It is also worth noting that the aryl fluoride products of crosscoupling have potential use in the construction of pharma-ceuticals, agrochemicals, and materials, many of which contain functionalized fluoroarenes.…”

Regioselective Acceptorless Dehydrogenative Coupling of N‐Heterocycles toward Functionalized Quinolines, Phenanthrolines, and Indoles

“…This would provide a simple way of generating these products, which are traditionally synthesized using stoichiometric organometallic reagents. [27] Satisfactorily, reacting 2 a and 7 a-e with TFP for 2 h followed by adding the catalyst 1 d afforded 8 a-f in excellent yields, regardless of the position of the substituents on the N-containing ring (Table 3).…”