Highly Selective Copper‐Catalyzed Asymmetric [3+2] Cycloaddition of Azomethine Ylides with Acyclic 1,3‐Dienes

The first examples of the catalytic asymmetric 1,3‐dipolar cycloaddition of azomethine ylides with acyclic activated 1,3‐dienes (and 1,3‐enynes) are described. Under copper catalysis, a selective cycloaddition at the terminal γ,δ‐C?C bond is observed. In addition, depending on the ligand used, either the exo or the endo adduct can be obtained with high selectivity. Under appropriate reaction conditions, the acyclic 1,6‐addition product is detected, suggesting a stepwise mechanism. The resulting C4‐alkenyl‐substituted pyrrolidines are suitable substrates for further access to polycyclic systems, as highlighted by the preparation of hexahydrochromeno[4,3‐b]pyrrole and the tetracyclic core of the alkaloid gracilamine.     

Beyond Stereoselectivity,Switchable Catalysis: Some of the Last Frontier Challenges in Ring‐Opening Polymerization of Cyclic Esters

Metal‐based catalysts and initiators have played a pivotal role in the ring‐opening polymerization (ROP) of cyclic esters, thanks to their high activity and remarkable ability to control precisely the architectures of the resulting polyesters in terms of molar mass, dispersity, microstructure, or tacticity. Today, after two decades of extensive research, the field is slowly reaching maturity. However, several challenges remain, while original concepts have emerged around new types or new applications of catalysis. This Review is not intended to comprehensively cover all of these aspects. Rather, it provides a personal overview of the very recent progress achieved in some selected, important aspects of ROP catalysis—stereocontrol and switchable catalysis. Hence, the first part addresses the development of new metal‐based catalysts for the isoselective ROP of racemic lactide towards stereoblock copolymers, and the use of syndioselective ROP metal catalysts to control the monomer sequence in copolymers. A second part covers the development of ROP catalysts—primarily metal‐based catalysts, but also organocatalysts—that can be externally regulated by the use of chemical or photo stimuli to switch them between two states with different catalytic abilities. Current challenges and opportunities are highlighted.     

Micromachining of circular ring microstructure by femtosecond laser pulses

In this paper, integration of interference phenomenon into femtosecond laser micromachining was reported as the femtosecond laser pulses were reshaped spatially to perform ablation. The generation of circular interference pattern was demonstrated by overlapping infrared femtosecond laser pulses. The interference pattern was subsequently focused on a copper substrate to ablate microstructures of concentric circular rings. The present technique is expected to open up new applications in the areas of rapid fabrication of micro-Fresnel lenses, hybrid microlenses and lens arrays.     

Estimation of multivariate binary density using orthogonal functions

In this paper, the authors studied certain properties of the estimate of Liang and Krishnaiah (1985, J. Multivariate Anal. 16, 162–172) for multivariate binary density. An alternative shrinkage estimate is also obtained. The above results are generalized to general orthonormal systems.     

A new solution of reducing polymer optical fiber losses

Polymethyl methacrylate (PMMA) is one of the most commonly used optical materials. However, the application of it in the area of optical communication is strongly limited by the intrinsic absorption loss of carbon-hydrogen stretching vibration. In this paper, we present a method to solve the problem by adopting the hollow-core fibers with cobweb cladding structure. The fibers use a single dielectric material and may solve the problem of structural support. Thus the feasibility of the “OmniGuide” fibers is improved, while a series of advantages of the “OmniGuide” hollow-core fiber are retained. It is promising that a fiber with low transmission loss, high bandwidth, large-core, and low costs can be designed and fabricated using PMMA. At the same time, a very broad range of the wavelengths (from visible to near infrared region, for instance, wavelengths at 0.65-1.12 μm, and even 1.30 μm, 1.54 μm and their neighbors) may be adopted for signal wavelength.