Cyclopropanes are key features in many preclinical, clinical, and commercial drugs, as well as natural products. The most prolific technique for their synthesis is the metal-catalyzed reaction of an alkene with a diazoalkane, a highly energetic reagent requiring stringent safety precautions. Discovery of alternative innocuous reagents remains an ongoing challenge. Herein, we report a simple photoredox-catalyzed intermolecular cyclopropanation of unactivated alkenes with active methylene compounds. The reaction proceeds in neutral solvent under air or dioxygen (O 2 ) with a photoredox catalyst excited by blue light-emitting diode light and an iodine co-catalyst that is either added as molecular iodine or generated in situ from alkyl iodides. Mechanistic investigations indicate that photosensitized O 2 plays a vital role in the generation of carbon-centered radicals for both the addition of active methylene compounds to alkenes and the ring closure.

Dendritic materials possessing urethane linkage are surprisingly more stable than similar structures having functional groups such as ether, ester, amide, or carbosilane. This generates profound interest in dendritic polyurethanes. Construction of a well-defined polyurethane dendrimer is, however, challenging because of isocyanates’ high reactivity. As a model of our ongoing dendrimer-research, herein, we report a protecting group-free one-pot multicomponent Curtius reaction to furnish a robust and versatile AB 2 -type dendron, which ensures late-stage modification of both the dendron and dendritic macromolecule yielding a surface functionalized polyurethane dendrimer. While 5-hydroxyisophthalic acid, 11-bromoundecanol, and 4-penten-1-ol were utilized in the construction of the dendron, thiol–ene click chemistry was employed for the late-stage modification. Novel dendrons and dendrimers synthesized were characterized by NMR (1D and 2D) and high-resolution MALDI-TOF analysis. This strategy allows an easy late-stage modification of dendritic macromolecules and is highly useful in the synthesis of both symmetrical and unsymmetrical dendrimers (Janus dendrimers).

One-pot multicomponent Curtius reaction afforded a versatile MN2 dendron. Late-stage modification of both dendron and dendrimer affords highly fluorescent dendrimers.

The construction of well-defined polyurethane dendrimers is challenging due to the high reactivity of externally added or in situ formed isocyanates leading to the formation of side products. With a primary focus of dendrimer research being the interaction of the periphery and the core, we report the synthesis of a common polyurethane dendron, which allows for the late-stage variation of both the periphery and the core. The periphery can be varied simply by installing a clickable unit in the dendron and then attaching to the core and vice-versa. Thus, a common dendron allows for varying periphery and core in the final two steps. To accomplish this, a protecting group-free, one-pot multicomponent Curtius reaction was utilized to afford a robust and versatile AB2 type polyurethane dendron employing commercially available simple molecules: 5-hydroxyisophthalic acid, 11-bromoundecanol, and 4-penten-1-ol. Subsequent late-stage modifications of either dendrons or dendrimers via a thiol-ene click reaction gave surface-functionalized alternating aromatic-aliphatic polyurethane homodendrimers to generation-three (G3). The dendrons and the dendrimers were characterized by NMR, mass spectrometry, and FT-IR analysis. A bifunctional AB2 type dendritic monomer demonstrated this approach’s versatility that can either undergo a thiol-ene click or attachment to the core. This approach enables the incorporation of functionalities at the periphery and the core that may not withstand the dendrimer growth for the synthesis of polyurethane dendrimers and other dendritic macromolecules.

Fluorescent dendrimers have wide applications in biomedical and materials science. Here, we report the synthesis of fluorescent polyurethane homodendrimers and Janus dendrimers, which often pose challenges due to the inherent reactivity of isocyanates. Polyurethane dendrons (G1-G3) were synthesized via a convergent method using a one-pot multicomponent Curtius reaction as a crucial step to establish urethane linkages. The alkyne periphery of the G1–G3 dendrons was modified by a copper catalyzed azide–alkyne click reaction (CuAAC) to form fluorescent dendrons. In the reaction of the surfaces functionalized two different dendrons with a difunctional core, a mixture of three dendrimers consisting of two homodendrimers and a Janus dendrimer were obtained. The Janus dendrimer accounted for a higher proportion in the products’ distribution, being as high as 93% for G3. The photophysical properties of Janus dendrimers showed the fluorescence resonance energy transfer (FRET) from one to the other fluorophore of the dendrimer. The FRET observation accompanied by a large Stokes shift make these dendrimers potential candidates for the detection and tracking of interactions between the biomolecules, as well as potential candidates for fluorescence imaging.