A C-H functionalization approach to diverse nitrogenous scaffolds through conjugate addition of catalytic allyliron nucleophiles.

Cyclopentadienyliron(ii) dicarbonyl complexes capable of coordinating to and enhancing the acidity of a range of unsaturated substrates have emerged as a new class of base-metal derived catalysts for C-H functionalization. In this manuscript, the iron-catalyzed C-H functionalization of allylic C(sp3)-H bonds using nitrogen containing α,ß-unsaturated carbonyl compounds as coupling partners is reported. Employing a cationic cyclopentadienyliron dicarbonyl complex, this redox neutral process converts simple alkenes into allylic anion equivalents for 1,4-addition into maleimides, acyclic α,ß-unsaturated imides, and vinylogous amides. The judicious pairing of pyridine and alkylamine bases with Lewis acid additives allowed each of these classes of substrates to be successfully employed, allowing for the formation of a diverse collection of cyclic and acyclic nitrogen-containing compounds featuring C-C unsaturation. The resulting Michael adducts can be further transformed into a variety of useful scaffolds such as allylated pyrroles, pyrrolidines, and carbocyclic acids.

Iron-Catalyzed Coupling of Alkenes and Enones: Sakurai-Michael-type Conjugate Addition of Catalytic Allyliron Nucleophiles.

The iron-catalyzed coupling of alkenes and enones through allylic C(sp3)-H functionalization is reported. This redox-neutral process employs a cyclopentadienyliron(II) dicarbonyl catalyst and simple alkene substrates to generate catalytic allyliron intermediates for 1,4-addition to chalcones and other conjugated enones. The use of 2,4,6-collidine as the base and a combination of triisopropylsilyl triflate and LiNTf2 as Lewis acids was found to facilitate this transformation under mild, functional group-tolerant conditions. Both electronically unactivated alkenes as well as allylbenzene derivatives could be employed as pronucleophilic coupling partners, as could a range of enones bearing electronically varied substituents.

Iron-Catalyzed Contrasteric Functionalization of Allenic C(sp2)-H Bonds: Synthesis of α-Aminoalkyl 1,1-Disubstituted Allenes.

An iron-catalyzed C-H functionalization of simple monosubstituted allenes is reported. An efficient protocol for this process was made possible by the use of a newly developed electron-rich and sterically hindered cationic cyclopentadienyliron dicarbonyl complex as the catalyst and N-sulfonyl hemiaminal ether reagents as precursors to iminium ion electrophiles. Under optimized conditions, the use of a mild, functional-group-tolerant base enabled the conversion of a range of monoalkyl allenes to their allenylic sulfonamido 1,1-disubstituted derivatives, a previously unreported and contrasteric regiochemical outcome for the C-H functionalization of electronically unbiased and directing-group-free allenes.