Performance of long-wave infrared band of microstructured heavily doped InAsSb on type II superlattice layer part 1: the photonic study.

This article deals with the optical study of nanostructured components which absorb light across the entire long-wave infrared (LWIR) spectral band. The components are made of type-II superlattice (T2SL) absorber and highly doped InAsSb, the latter being nanostructured to ensure multiple resonances. We studied two components: in the first one, the T2SL has a thickness of 1.6 µm, and in the second its thickness is 300 nm. The calculated absorption spectra were shown and the components revealed high absorption thanks to optical resonance and high angular acceptance. A fabrication process has been developed, and optical measurements have confirmed the reliability of the model.

Interband cascade lasers grown simultaneously on GaSb, GaAs and Si substrates.

We report on Sb-based interband cascade lasers simultaneously grown on GaSb, GaAs and Si substrates. 8 µm x 2 mm devices exhibited similar threshold currents around 40 mA at 20°C and achieved continuous-wave (CW) operation up to 65°C on GaSb, GaAs and Si substrates despite a dislocation density of ∼ 4.108 cm-2 for both mismatched substrates. In the CW regime the output power of the devices emitting at 3.3 µm exceeded 30 mW/facet at 20°C. ICLs on GaAs and Si were subsequently aged at 50°C with an injection current of 200 mA, i.e. five times the laser-threshold current. No degradation was observed after 500 h of CW operation, demonstrating the high performance of ICLs and their tolerance to dislocations.

Enantioselective Synthesis of Heteroatom-Linked Non-Biaryl Atropisomers.

Atropisomers hold significant fascination, not only for their prevalence in natural compounds but also for their biological importance and wide-ranging applications as chiral materials, ligands, and organocatalysts. While biaryl and heterobiaryl atropisomers are commonly studied, the enantioselective synthesis of less abundant heteroatom-linked non-biaryl atropisomers presents a formidable challenge in modern organic synthesis. Unlike classical atropisomers, these molecules allow rotation around two bonds, resulting in low barriers to enantiomerization through concerted bond rotations. In recent years the discovery of new configurationally stable rare non-biaryl scaffolds such as aryl amines, aryl ethers and aryl sulfones as well as innovative methodologies to control their configuration have been disclosed in the literature and constitute the topic of this minireview.

Enantioselective Organocatalysis and Superacid Activation: Challenges and Opportunities.

Since the pioneer reports of the groups of Akiyama and Terada on Brønsted acid organocatalysis, this field never stopped growing with the development of ingenious strategies for the activation of challenging poorly reactive substrates. The development of superacidic organocatalysts is an important way to selectively functionalize reluctant electrophiles and other approaches have also emerged such as the combination of Lewis and Brønsted acids as well as the consecutive organocatalysis and superacid activation. This Concept aims to highlight these different strategies and demonstrate their complementarity.

Enantioselective Synthesis of Atropisomers by Oxidative Aromatization with Central-to-Axial Conversion of Chirality.

Atropisomers are fascinating objects of study by themselves for chemists but also find applications in various sub-fields of applied chemistry. Obtaining them in enantiopure form is far from being a solved challenge, and the past decades has seen a surge of methodological developments in that direction. Among these strategies, oxidative aromatization with central-to-axial conversion of chirality has gained increasing popularity. It consists of the oxidation of a cyclic non-aromatic precursors into the corresponding aromatic atropisomers. This review proposes a critical analysis of this research field by delineating it and discussing its historical background and its present state of the art to draw potential future development directions.

Hidden Heptacyclic Chiral N-Acyl Iminium Ions: A New Entry to Enantioenriched Polycyclic Azepanes and Azocanes by Superacid-Promoted Intramolecular Pictet-Spengler Reaction.

Enantioenriched complex fused-tricyclic azepanes or bridged-polycyclic azocanes were constructed via a two-step sequence involving an enantioselective organocascade followed by superacid activation of the domino adduct. The activated oxa-bridged azepane acts as a key hidden heptacyclic chiral N-acyl iminium ion triggering a chemo- and diastereoselective intramolecular mono- or di-arylation.

Enantioselective Synthesis of Acyclic Stereotriads Featuring Fluorinated Tetrasubstituted Stereocenters.

Elaboration of enantioenriched complex acyclic stereotriads represents a challenge for modern synthesis even more when fluorinated tetrasubstituted stereocenters are targeted. We have been able to develop a simple strategy in a sequence of two unprecedented steps combining a diastereoselective aldol-Tishchenko reaction and an enantioselective organocatalyzed kinetic resolution. The aldol-Tishchenko reaction directly generates a large panel of acyclic 1,3-diols possessing a fluorinated tetrasubstituted stereocenter by condensation of fluorinated ketones with aldehydes under very mild basic conditions. The anti 1,3-diols featuring three contiguous stereogenic centers are generated with excellent diastereocontrol (typically >99 : 1 dr). Depending upon the precursors both diastereomers of stereotriads are accessible through this flexible reaction. Furthermore, from the obtained racemic scaffolds, development of an organocatalyzed kinetic resolution enabled to generate the desired enantioenriched stereotriads with excellent selectivity (typically er >95 : 5).

Enantiospecific Syntheses of Congested Atropisomers through Chiral Bis(aryne) Synthetic Equivalents.

The synthetic equivalents of the enantiopure binaphthyl bis(aryne) atropisomers derived from BINOL (1,1'-bi-2,2'-naphtol) featuring a stereogenic axis vicinal to the two reactive triple bonds can be generated for the first time in solution in an enantiospecific manner. Using a two-step sequence based on the bidirectional [4+2] cycloaddition of furan derivatives followed by an aromatizative deoxygenation reaction, several 9,9'-bianthracenyl-based atropisomers could be prepared enantiospecifically in high enantiomeric purity. Alternatively, bidirectional reactions with anthracene, 2-bromostyrene, and perylene as the arynophiles afforded very congested bis(benzotriptycene), bis(tetraphene) and bis(anthra[1,2,3,4-ghi]perylene) nanocarbon atropisomers in equally high enantiomeric purity. In complement, cross reactions with two different arynophiles revealed possible. The unusual atropisomer prototypes described in this study open the way to enantiopure nanographene atropisomers designed for functions.

Determination of the Rate Constant of the [4 + 2] Cycloaddition Between an Aryne Atropisomer and Furan in Solution.

Using a specially designed prototype of a nonracemic aryne atropisomer with a low barrier to enantiomerization (ca. 36 kJ·mol-1), it was possible to determine the kinetic constant of its cycloaddition with furan in solution by a combination of theoretical calculations and experimental measurements. It was found that the reaction half-life of this aryne atropisomer in solution with 100 equivalents of furan as the trapping reagent is <150 ns at temperatures above -20 °C.

COVID-19 among Amazonian indigenous in Peru: mortality, incidence, and clinical characteristics.

BACKGROUND: Few studies have described the clinical characteristics of patients with COVID-19 from ethnic minority groups. Our objective was to evaluate the mortality and incidence rates, clinical characteristics and factors associated with mortality in cases with COVID-19 belonging to the Amazonian indigenous ethnic group in Peru. METHODS: We performed a retrospective cohort study including all cases from COVID-19 among Peruvian people identified as Amazonian indigenous from 07 March to 31 October 2020. We calculated the standardized mortality and incidence ratios using the indirect age-adjusted method to determine the differences between Amazonian Indigenous and the general population. In addition, we used multivariable logistic regression to determine the risk factors for death. RESULTS: A total of 19 018 laboratory confirmed COVID-19 cases were analyzed. Indigenous people had 3.18 (95% CI, 3.13-3.23) times the risk of infection and 0.34 (0.31-0.37) times the mortality risk of the general Peruvian population. Males had 1.29 (1.04-1.61) times the odds of death compared with females and for each year of age, the odds of mortality increased 1.03 (1.03-1.04) times. Cases with respiratory distress had 2.47 (1.96-3.10) times more likely to die. Having an immunodeficiency was 18.7 (6.12-57.00) times more likely to die. DISCUSSION: The Amazonian indigenous population in Peru was strongly affected by COVID-19 compared with the general Peruvian population.

GaSb-based laser diodes grown on MOCVD GaAs-on-Si templates.

We report GaSb-based laser diodes (LDs) grown on on-axis (001) Si substrates and emitting at 2.3 µm. Two series of LDs were studied and compared. For the first series, a GaAs-based buffer layer was first grown by metal organic chemical vapor deposition (MOCVD) before growing the laser heterostructure by molecular-beam epitaxy (MBE). For the second series, a MOCVD GaSb buffer layer was added between the MOCVD GaAs buffer layer and the MBE laser heterostructure. Both series of LDs exhibited threshold currents in the 50-100 mA range and several mW output power at room temperature. They demonstrated continuous wave operation (CW) up to 70°C (set-up limited) without thermal rollover. Broad area LDs exhibited record threshold-current densities in the 250-350 A.cm-2 range for the second series of LDs, in spite of cracks that appeared during device processing. These results show that the design and fabrication steps of the buffer-layer stacks are critical issues in the epitaxial integration of GaSb-based optoelectronic devices on Si substrates and offer room for much performance improvement.

Enantiospecific Generation and Trapping Reactions of Aryne Atropisomers.

Enantioenriched aryne atropisomers having a biaryl stereogenic axis vicinal to the reactive triple bond are demonstrated to exist. These reaction intermediates are easily produced in situ and can undergo the standard aryne cycloaddition chemistry in an enantiospecific manner. Notably, the aryne atropisomers herein have allowed the practical syntheses of a small nanographene as well as some triptycene and anthracene derivatives that embed stereogenic axes of controlled absolute configurations.

Simultaneous Control of Central and Helical Chiralities: Expedient Helicoselective Synthesis of Dioxa[6]helicenes.

An expedient synthesis of a new family of configurationally stable dioxa[6]helicenes was established using a sequential helicoselective organocatalyzed heteroannulation/eliminative aromatization via enantioenriched fused 2-nitro dihydrofurans featuring both central and helical chiralities. Starting from simple achiral precursors, a broad range of these previously unknown chiral heterocyclic scaffolds were obtained with good efficiency, and their aromatization proceeded with very high enantiopurity retention in most cases.

Etched-cavity GaSb laser diodes on a MOVPE GaSb-on-Si template.

We report on 2.3-µm etched-cavity GaSb-based laser diodes (LDs) epitaxially integrated on on-axis (001)Si and benchmarked against their cleaved facet counterparts. The LDs were grown in two steps. First, a GaSb-on-Si template was grown by metal-organic vapor phase epitaxy (MOVPE) before the growth of the LD heterostructure by molecular-beam epitaxy. Different etched-facet geometries operate in continuous wave well above room temperature, and their performance are similar to those of cleaved-cavity LDs. These results show that etching mirrors is a viable route to form laser cavities in the GaSb technology and that MOVPE GaSb-on-Si templates are a suitable platform for optoelectronic devices overgrowth.

Periselectivity in the aza-Diels-Alder Cycloaddition between α-Oxoketenes and N-(5-Pyrazolyl)imines: A Combined Experimental and Theoretical Study.

The thermal 6π aza-Diels-Alder cycloadditions between α-oxoketenes, in situ derived from a thermally induced Wolff rearrangement of 2-diazo-1,3-diketones, and N-(5-pyrazolyl)imines as prototypical electron-rich 2-azadienes lead to two distinct sets of products, essentially as a function of the nature of the α-oxoketenes involved. For instance, cyclic five-membered α-oxoketenes lead preferentially to spiro hydropyridin-4-ones, which involves the α-oxoketenes as the 2π partners at their C═C double bond and the N-(5-pyrazolyl)imines as the 4π partners at their 2-azadiene moiety. In contrast, other cyclic and acyclic α-oxoketenes lead preferentially to 1,3-oxazin-4-ones, which now involves the α-oxoketenes as the 4π partners at their 1-oxadiene moiety and the N-(5-pyrazolyl)imines as the 2π partners at their C═N double bond. A computational modeling study using DFT methods allowed rationalizing this change of periselectivity: the formation of spiro hydropyridin-4-ones is under thermodynamic control while the formation of 1,3-oxazin-4-ones is kinetically controlled, and slightly thermodynamically disfavored in the five-membered ring series. The competing cyclodimerization of the α-oxoketenes is also studied in detail.

Organocatalytic carbon dioxide fixation to epoxides by perfluorinated 1,3,5-triols catalysts.

In order to improve epoxides conversion to carbonates by fixation of CO2 a new type of perfluorinated triol catalysts was developed. These simple acyclic scaffolds of enhanced acidity are efficient for catalysis through selective H-bonding activation of the epoxide. In combination with TBAI as co-catalyst, this useful transformation is performed under only 1 atmosphere of CO2 and between 30 to 80 °C. Both the 1,3,5-triol motif and the perfluorinated side chains are crucial in order to observe this epoxide opening under such mild conditions. In addition, the stereochemistry of the starting epoxide can efficiently be conserved during the carbonate formation.

Catalytic strategies towards 1,3-polyol synthesis by enantioselective cascades creating multiple alcohol functions.

This review highlights the different enantioselective catalyst-controlled cascades creating multiple alcohol functions through the formation of several carbon-carbon bonds. Through subsequent simple derivatization, these strategies ensure the rapid preparation of 1,3-polyols. Thanks to the use of efficient metal- or organo-catalysts, these cascades enable the selective assembly of multiple substrates considerably limiting operations and waste generation. For this purpose, several mono- or bi-directional approaches have been devised allowing successive C-C bond-forming events. The considerable synthetic economies these cascades enable have been demonstrated in the preparation of a wide variety of complex bioactive natural products, notably polyketides.

Periselectivity in the Aza-Diels-Alder Reaction of 1-Azadienes with α-Oxoketenes: A Combined Experimental and Theoretical Study.

Inversions in the periselectivity of formal aza-Diels-Alder cycloadditions between α-oxoketenes generated by a thermally-induced Wolff rearrangement and 1-azadienes were observed experimentally as a function of the α-oxoketene and the 1-azadiene, as well as the reaction temperature and time. Some unexpected inversion in the diastereoselectivity was observed, too. These variations in selectivities were fully rationalized by computational modeling using density functional theory (DFT) methods.

Enantioselective Synthesis of Atropisomers with Multiple Stereogenic Axes.

Atropisomers possessing multiple stereogenic axes are intriguing molecules with huge potential. However, only few approaches for their enantioselective synthesis are available due to the difficulties in assembling various stereogenic axes with high enantiocontrol. Only recently, innovative methods have emerged, opening new possibilities for the synthesis of this original class of atropisomeric compounds. This Minireview describes the development of this field based on a classification of the multi-axis systems according to the distance between the stereogenic axes and the strategy used to build them.

Enantioenriched Methylene-Bridged Benzazocanes Synthesis by Organocatalytic and Superacid Activations.

Achieving in a straightforward way the synthesis of enantioenriched elaborated three-dimensional molecules related to bioactive natural products remains a long-standing quest in organic synthesis. Enantioselective organocatalysis potentially offers a unique opportunity to solve this problem, especially when combined with complementary modes of activation. Here, we report the sequential association of organocatalytic and superacid activations of simple linear achiral readily available precursors to promote the formation of unique highly elaborated chiral methylene-bridged benzazocanes exhibiting three to five fully-controlled stereocenters. This peculiar backbone, difficult to assemble by standard synthetic approaches, is closely related to bioactive natural and synthetic morphinans and benzomorphans. The formation of a highly reactive chiral 7-membered ring N-acyl iminium superelectrophilic ion, evidenced by low-temperature in situ NMR experiments, triggers a challenging stereoselective Friedel-Crafts-type cyclization.