1,3-Difunctionalization of [1.1.1]propellane through iron-hydride catalyzed hydropyridylation.

Current methodologies for the functionalization of [1.1.1]propellane primarily focus on achieving 1, 3-difunctionalized bicyclo[1.1.1]pentane or ring-opened cyclobutane moiety. Herein, we report an innovative approach for the 1, 3-difunctionalization of [1.1.1]propellane, enabling access to a diverse range of highly functionalized cyclobutanes via nucleophilic attack followed by ring opening and iron-hydride hydrogen atom transfer. To enable this method, we developed an efficient iron-catalyzed hydropyridylation of various alkenes for C - H alkylation of pyridines at the C4 position, eliminating the need for stoichiometric quantities of oxidants or reductants. Mechanistic investigations reveal that the resulting N-centered radical serves as an effective oxidizing agent, facilitating single-electron transfer oxidation of the reduced iron catalyst. This process efficiently sustains the catalytic cycle, offering significant advantages for substrates with oxidatively sensitive functionalities that are generally incompatible with alternative approaches. The strategy presented herein is not only mechanistically compelling but also demonstrates broad versatility, highlighting its potential for late-stage functionalization.

Remote C-H Pyridylation of Hydroxamates through Direct Photoexcitation of O-Aryl Oxime Pyridinium Intermediates.

Herein, we report an efficient strategy for the remote C-H pyridylation of hydroxamates with excellent ortho-selectivity by designing a new class of photon-absorbing O-aryl oxime pyridinium salts generated in situ from the corresponding pyridines and hydroxamates. When irradiated by visible light, the photoexcitation of oxime pyridinium intermediates generates iminyl radicals via the photolytic N-O bond cleavage, which does not require an external photocatalyst. The efficiency of light absorption and N-O bond cleavage of the oxime pyridinium salts can be modulated through the electronic effect of substitution on the O-aryl ring. The resultant iminyl radicals enable the installation of pyridyl rings at the γ-CN position, which yields synthetically valuable C2-substituted pyridyl derivatives. This novel synthetic approach provides significant advantages in terms of both efficiency and simplicity and exhibits broad functional group tolerance in complex settings under mild and metal-free conditions.

A novel physical unclonable function (PUF) using 16 × 16 pure-HfOxferroelectric tunnel junction array for security applications.

As the computing paradigm has shifted toward edge computing, improving the security of edge devices is attracting significant attention. However, because edge devices have limited resources in terms of power and area, it is difficult to apply a conventional cryptography system to protect them. On the other hand, as a simple security application, a physical unclonable function (PUF) can be implemented without power and area problems because it provides a security key by utilizing process variations without additional external circuits. Ferroelectric tunnel junctions (FTJs) are 2-terminal devices that store information by changing the resistance of a ferroelectric material, where the resistance is determined by the polarization states of the ferroelectric domains. Because polycrystalline ferroelectric materials have a multi-domain nature, domain variation can also be used as a randomness source to induce cell-to-cell variations along with process variations. In this paper, we demonstrate PUF operations of a low-power, small area 16 × 16 hafnium oxide (pure-HfOx)-based FTJ array using certain metrics. It is clear that the proposed array consisting of scaled FTJs has adequate randomness for security applications such that the array-level PUF operations are robust against model-based machine learning attacks.

Investigation on Ambipolar Current Suppression Using a Stacked Gate in an L-shaped Tunnel Field-Effect Transistor.

L-shaped tunnel field-effect transistor (TFET) provides higher on-current than a conventional TFET through band-to-band tunneling in the vertical direction of the channel. However, L-shaped TFET is disadvantageous for low-power applications because of increased off-current due to the large ambipolar current. In this paper, a stacked gate L-shaped TFET is proposed for suppression of ambipolar current. Stacked gates can be easily implemented using the structural features of L-shaped TFET, and on- and off-current can be controlled separately by using different gates located near the source and the drain, respectively. As a result, the suppression of ambipolarity is observed with respect to work function difference between two gates by simulation of the band-to-band tunneling generation. Furthermore, the proposed device suppresses ambipolar current better than existing ambipolar current suppression methods. In particular, low drain resistance is achieved as there is no need to reduce drain doping, which leads to a 7% enhanced on-current. Finally, we present the fabrication method for a stacked gate L-shaped TFET.