Although generally considered competitive, the alkenylation and carbonyl olefination routes to alkenes are also complementary. In this Account, we focus on these approaches for the synthesis of regio- and stereodefined di- and trisubstituted alkenes and a few examples of tetrasubstituted alkenes. We also discuss the subset of regio- and stereodefined dienes and oligoenes that are conjugated. Pd-catalyzed cross-coupling using alkenyl metals containing Zn, Al, Zr, and B (Negishi coupling and Suzuki coupling) or alkenyl halides and related alkenyl electrophiles provides a method of alkenylation with the widest applicability and predictability, with high stereo- and regioselectivity. The requisite alkenyl metals or alkenyl electrophiles are most commonly prepared through highly selective alkyne addition reactions including (i) conventional polar additions, (ii) hydrometalation, (iii) carbometalation, (iv) halometalation, and (v) other heteroatom-metal additions. Although much more limited in applicability, the Heck alkenylation offers an operationally simpler, viable alternative when it is highly selective and satisfactory. A wide variety of carbonyl olefination reactions, especially the Wittig olefination and its modifications represented by the E-selective HWE olefination and the Z-selective Still-Gennari olefination, collectively offer the major alternative to the Pd-catalyzed alkenylation. However, the carbonyl olefination method fundamentally suffers from more limited stereochemical options and generally lower stereoselectivity levels than the Pd-catalyzed alkenylation. In a number of cases, however, very high (>98%) stereoselectivity levels have been attained in the syntheses of both E and Z isomers. The complementarity of the alkenylation and carbonyl olefination routes provide synthetic chemists with valuable options. While the alkenylation involves formation of a C-C single bond to a CC bond, the carbonyl olefination converts a CO bond to a CC bond. When a precursor to the desired alkene is readily available as an aldehyde, the carbonyl olefination is generally the more convenient of the two. This is a particularly important factor in many cases where the desired alkene contains an allylic asymmetric carbon center, since alpha-chiral aldehydes can be prepared by a variety of known asymmetric methods and readily converted to allylically chiral alkenes via carbonyl olefination. On the other hand, a homoallylically carbon-branched asymmetric center can be readily installed by either Pd-catalyzed isoalkyl-alkenyl coupling or Zr-catalyzed asymmetric carboalumination (ZACA reaction) of 1,4-dienes. In short, it takes all kinds to make alkenes, just as it takes all kinds to make the world.
Layered kagome-lattice 3 d transition metals are emerging as an exciting platform to explore the frustrated lattice geometry and quantum topology. However, the typical kagome electronic bands, characterized by sets of the Dirac-like band capped by a phase-destructive flat band, have not been clearly observed, and their orbital physics are even less well investigated. Here, we present close-to-textbook kagome bands with orbital differentiation physics in CoSn, which can be well described by a minimal tight-binding model with single-orbital hopping in Co kagome lattice. The capping flat bands with bandwidth less than 0.2 eV run through the whole Brillouin zone, especially the bandwidth of the flat band of out-of-plane orbitals is less than 0.02 eV along Γ− M . The energy gap induced by spin-orbit interaction at the Dirac cone of out-of-plane orbitals is much smaller than that of in-plane orbitals, suggesting orbital-selective character of the Dirac fermions.
The Majorana fermion, which is its own anti-particle and obeys non-abelian statistics, plays a critical role in topological quantum computing. It can be realized as a bound state at zero energy, called a Majorana zero mode (MZM), in the vortex core of a topological superconductor, or at the ends of a nanowire when both superconductivity and strong spin orbital coupling are present. A MZM can be detected as a zero-bias conductance peak (ZBCP) in tunneling spectroscopy. However, in practice, clean and robust MZMs have not been realized in the vortices of a superconductor, due to contamination from impurity states or other closely-packed Caroli-de Gennes-Matricon (CdGM) states, which hampers further manipulations of MZMs. Here using scanning tunneling spectroscopy, we show that a ZBCP well separated from the other discrete CdGM states exists ubiquitously in the cores of free vortices in the defect free regions of (Li0.84Fe0.16)OHFeSe, which has a superconducting transition temperature of 42 K. Moreover, a Dirac-cone-type surface state is observed by angle-resolved photoemission spectroscopy, and its topological nature is confirmed by band calculations. The observed ZBCP can be naturally attributed to a MZM arising from this chiral topological surface states of a bulk superconductor. (Li0.84Fe0.16)OHFeSe thus provides an ideal platform for studying MZMs and topological quantum computing. 2
Kagome-lattices of 3d-transition metals hosting Weyl/Dirac fermions and topological flat bands exhibit non-trivial topological characters and novel quantum phases, such as the anomalous Hall effect and fractional quantum Hall effect. With consideration of spin–orbit coupling and electron correlation, several instabilities could be induced. The typical characters of the electronic structure of a kagome lattice, i.e., the saddle point, Dirac-cone, and flat band, around the Fermi energy (EF) remain elusive in magnetic kagome materials. We present the experimental observation of the complete features in ferromagnetic kagome layers of YMn6Sn6 helically coupled along the c-axis, by using angle-resolved photoemission spectroscopy and band structure calculations. We demonstrate a Dirac dispersion near EF, which is predicted by spin-polarized theoretical calculations, carries an intrinsic Berry curvature and contributes to the anomalous Hall effect in transport measurements. In addition, a flat band and a saddle point with a high density of states near EF are observed. These multi-sets of kagome features are of orbital-selective origin and could cause multi-orbital magnetism. The Dirac fermion, flat band and saddle point in the vicinity of EF open an opportunity in manipulating the topological properties in magnetic materials.
With increasing life expectations, more and more patients suffer from fractures either induced by intensive sports or other bone-related diseases. The balance between osteoblast-mediated bone formation and osteoclast-mediated bone resorption is the basis for maintaining bone health. Osterix (Osx) has long been known to be an essential transcription factor for the osteoblast differentiation and bone mineralization. Emerging evidence suggests that Osx not only plays an important role in intramembranous bone formation, but also affects endochondral ossification by participating in the terminal cartilage differentiation. Given its essentiality in skeletal development and bone formation, Osx has become a new research hotspot in recent years. In this review, we focus on the progress of Osx’s function and its regulation in osteoblast differentiation and bone mass. And the potential role of Osx in developing new therapeutic strategies for osteolytic diseases was discussed.
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