ABSTRACT
Controlling regioselectivity in C-H functionalizations is a key challenge in chemical method development. In arenes, functionalizations are most difficult to direct towards the C-H group furthest away from a substituent, in its para position. We herein demonstrate how the para-C-H arylation of anilines with non-activated aryl halides, elusive to date, is achieved by a base-assisted "metalla-tautomerism" approach. A proton is abstracted from the aniline substrate and replaced by an arylpalladium species, generated from the aryl halide coupling partner. In this step, the palladium is directed away from the N- to the tautomeric para-C-H position by a large phosphine ligand combined with a triphenylmethyl shielding group. The triphenylmethyl group is easily installed and removed, and can be recycled.
ABSTRACT
Genuinely non-Hermitian topological phases can be realized in open systems with sufficiently strong gain and loss; in such phases, the Hamiltonian cannot be deformed into a gapped Hermitian Hamiltonian without energy bands touching each other. Comparing Green functions for periodic and open boundary conditions we find that, in general, there is no correspondence between topological invariants computed for periodic boundary conditions, and boundary eigenstates observed for open boundary conditions. Instead, we find that the non-Hermitian winding number in one dimension signals a topological phase transition in the bulk: It implies spatial growth of the bulk Green function.
ABSTRACT
Voigt points represent propagation directions in anisotropic crystals along which optical modes degenerate, leading to a single circularly polarized eigenmode. They are a particular class of exceptional points. Here, we report the fabrication and characterization of a dielectric, anisotropic optical microcavity based on nonpolar ZnO that implements a non-Hermitian system and mimics the behavior of Voigt points in natural crystals. We prove the exceptional-point nature by monitoring the complex-square-root topology of the mode eigenenergies (real and imaginary parts) around the Voigt points. Polarization state analysis shows that these artificially engineered Voigt points behave as vortex cores for the linear polarization and sustain chiral modes. Our findings apply to any planar microcavity with broken cylindrical symmetry and, thus, pave the way for exploiting exceptional points in widespread optoelectronic devices such as vertical cavity surface emitting lasers and resonant cavity light emitting diodes.
ABSTRACT
Herein we present the synthesis of symmetrically and unsymmetrically substituted 1,3-bissulfanylbicyclo[1.1.1]pentanes from disulfides and [1.1.1]propellane. Bicyclo[1.1.1]pentanes (BCPs) recently gained interest as rigid linkers and as bioisosters of para-substituted benzene and alkyne moieties. The most promising precursor for BCPs is [1.1.1]propellane (1). The available methods to synthesize BCPs are quite limited and many groups contribute to the development of novel methods. The insertion of 1 into disulfide bonds is known, but has never been thoroughly investigated. In this study, we show that an UV initiated radical reaction can be used to synthesize symmetrically and unsymmetrically substituted BCP sulfides by reaction of [1.1.1]propellane (1) with disulfides. Depending on the ratio of 1 to the disulfide, only the BCP product (with up to 98% yield) or a mixture of BCP and [2]staffane can be obtained. The reaction tolerates functional groups such as halogens, alkyl and methoxy groups. The separation of the corresponding BCP and [2]staffane products is challenging but possible by column chromatography and preparative TLC in most cases. Single crystal X-ray diffraction analysis confirms the rod-like structure of the [2]staffanes that is often required in material applications.
