Enantioselective Amino- and Oxycyanation of Alkenes via Organic Photoredox and Copper Catalysis.

The ß-amino nitrile moiety and its derivatives frequently appear in natural product synthesis, in drug design, and as ligands in asymmetric catalysis. Herein, we describe a direct route to these complex motifs through the amino- and oxycyanation of olefins utilizing an acridinium photooxidant in conjunction with copper catalysis. The transformation can be rendered asymmetric by using a serine-derived bisoxazoline ligand. Mechanistic studies implicate olefin-first oxidation. The scope of amines for the aminocyanation reaction has been greatly expanded by undergoing a cation radical intermediate as opposed to previous N-centered radical-initiated aminocyanations. Furthermore, alkyl carboxylic acids were included as nucleophiles in this type of transformation for the first time without any decarboxylative side reactions.

DBU-Promoted Cascade Annulation of Nitroarylcyclopropane-1,1-dicarbonitriles and 3-Aryl-2-cyanoacrylates: An Access to Highly Functionalized Cyclopenta[ b]furan Derivatives.

A DBU-promoted cascade annulation of nitroarylcyclopropane-1,1-dicarbonitriles and 3-aryl-2-cyanoacrylates for the synthesis of highly functionalized cyclopenta[ b]furan derivatives is described. High stereoselectivity, fused cyclopentane and furan can be established in a single reaction, highlighting the high efficiency and step-economy of this protocol. This reaction offers a novel and straightforward protocol to the synthesis of cyclopenta[ b]furans featuring the [3 + 2] cycloadditions of nitroarylcyclopropane-1,1-dicarbonitriles with 3-aryl-2-cyanoacrylates.

DBU-mediated [4 + 1] annulations of donor-acceptor cyclopropanes with carbon disulfide or thiourea for synthesis of 2-aminothiophene-3-carboxylates.

DBU-mediated [4 + 1] annulations of donor-acceptor cyclopropanes with carbon disulfide or thiourea to form 2-aminothiophene-3-carboxylate derivatives have been discovered. This reaction proceeds via the ring opening of donor-acceptor cyclopropanes to produce a 2-(iminomethylene)but-3-enoate intermediate, followed by the attack of an S-nucleophile for regioselective intermolecular nucleophilic addition, intramolecular S-nucleophilic addition, and final aromatization. A variety of functional groups could be tolerated under the reaction conditions.

Divergent Functionalization of Alkynes Enabled by Organic Photoredox Catalysis.

Direct functionalization of alkynes under oxidative conditions is challenging, as alkynes are usually recalcitrant towards typical oxidants. Herein, we communicate a strategy for the divergent functionalization of alkynes with photoexcited acridinium organic dyes, presumably via the formation of vinyl cation radicals as key intermediates. Based on the nature of the nucleophiles, different types of difunctionalized products were obtained in moderate to good yields. Addition of lithium Lewis acids resulted in a surprising reversal of diastereocontrol.

Aliphatic C-H Functionalization Using Pyridine N-Oxides as H-Atom Abstraction Agents.

The alkylation and heteroarylation of unactivated tertiary, secondary, and primary C(sp3)-H bonds was achieved by employing an acridinium photoredox catalyst along with readily available pyridine Noxides as hydrogen atom transfer (HAT) precursors under visible light. Oxygen-centered radicals, generated by single-electron oxidation of the Noxides, are the proposed key intermediates whose reactivity can be easily modified by structural adjustments. A broad range of aliphatic C-H substrates with electron-donating or -withdrawing groups as well as various olefinic radical acceptors and heteroarenes were well tolerated.