Formal Umpolung Addition of Phosphites to 2-Azaaryl Ketones under Chiral Brønsted Base Catalysis: Enantioselective Protonation Utilizing [1,2]-Phospha-Brook Rearrangement

The formal enantioselective umpolung addition of dialkyl phosphites to 2-azaaryl ketones was developed under Brønsted base catalysis. The reaction involves the enantioselective protonation of the transient α-oxygenated (2-azaaryl)methyl anion generated through the 1,2-addition of the anion of dialkyl phosphite to the 2-azaaryl ketone and the subsequent [1,2]-phospha-Brook rearrangement. A chiral bis(guanidino)iminophosphorane organosuperbase efficiently catalyzed the reaction to provide enantio-enriched phosphates in high yields with good to high enantioselectivities. This is a rare example of the catalytic enantioselective protonation of transient carbanions other than enolates, constructing a trisubstituted stereogenic center α to 2-azaarenes.     

Modulating the ground state,stability and charge transport in OFETs of biradicaloid hexahydro-diindenopyrene derivatives and a proposed method to estimate the biradical character

Biradicaloid compounds with an open-shell ground state have been the subject of intense research in the past decade. Although diindenoacenes are one of the most developed families, only a few examples have been reported as active layers in organic field-effect transistors (OFETs) with a charge mobility of around 10⁻³ cm² V⁻¹ s⁻¹ due to a steric disadvantage of the mesityl group to kinetically stabilize compounds. Herein, we disclose our efforts to improve the charge transport of the diindenoacene family based on hexahydro-diindenopyrene (HDIP) derivatives with different annelation modes for which the most reactive position has been functionalized with (triisopropylsilyl)ethynyl (TIPS) groups. All the HDIP derivatives show remarkably higher stability than that of TIPS-pentacene, enduring for 2 days to more than 30 days, which depends on the oxidation potential, the contribution of the singlet biradical form in the ground state and the annelation mode. The annelation mode affects not only the band gap and the biradical character (y₀) but also the value of the singlet–triplet energy gap (ΔE_S–T) that does not follow the reverse trend of y₀. A method based on comparison between experimental and theoretical bond lengths has been disclosed to estimate y₀ and shows that y₀ computed at the projected unrestricted Hartree–Fock (PUHF) level is the most relevant among those reported by all other methods. Thanks to their high stability, thin-film OFETs were successfully fabricated. Well balanced ambipolar transport was obtained in the order of 10⁻³ cm² V⁻¹ s⁻¹ in the bottom-gate/top-contact configuration, and unipolar transport in the top-gate/bottom-contact configuration was obtained in the order of 10⁻¹ cm² V⁻¹ s⁻¹ which is the highest value obtained for biradical compounds with a diindenoacene skeleton.

Biradicaloid HDIP derivatives show that the ΔE_S–T gap does not follow the reverse trend of the biradical character but depends more on the delocalization of the radical centres at the outer rings.     

Total Synthesis of Zephycarinatines via Photocatalytic Reductive Radical ipso-Cyclization

We report herein a nonbiomimetic strategy for the total synthesis of the plicamine-type alkaloids zephycarinatines C and D. The key feature of the synthesis is a stereoselective reductive radical ipso-cyclization using visible-light-mediated photoredox catalysis. This cyclization enabled the construction of a 6,6-spirocyclic core structure through the addition of a carbon-centered radical onto the aromatic ring. Biological evaluation of zephycarinatines and their derivatives revealed that the synthetic derivative with a keto group displays moderate inhibitory activity against LPS-induced NO production. This approach could offer future opportunities to expand the chemical diversity of plicamine-type alkaloids as well as providing useful intermediates for their syntheses.     

Scalable Total Syntheses and Structure–Activity Relationships of Haouamines A,B, and Their Derivatives as Stable Formate Salts

Haouamines A, B, and their derivatives were synthesized via Suzuki–Miyaura coupling and three key cyclization reactions as follows: the newly developed palladium(0)-catalyzed arylative cyclization of phenylalanine-derived alkyne–aldehydes with 2-bromoarylboronic acid (an “anti-Wacker”-type cyclization); BF₃ ⋅ OEt₂-promoted Friedel–Crafts-type cyclization of symmetrical electron-rich aromatic rings adjacent to a tertiary allylic alcohol leading to the indeno-tetrahydropyridine skeleton; and (cyanomethyl)trimethylphosphonium iodide-mediated macrocyclization of amino alcohols to afford aza-paracyclophane precursors. The palladium-catalyzed reduction of mono- and di-triflate intermediates in the later stages enabled the alteration of both the position and number of hydroxyl groups on the C-ring. The instability of haouamine B was dramatically improved by salt formation with formic acid. An unambiguous evaluation of the cytotoxicity of the prepared haouamine derivative formates with and without hydroxyl groups at different positions on the C-ring indicated that the catechol structure in haouamine B produced weak cytotoxicity.     

Chiral Dinuclear EuIII,TbIII, and YIII Complexes Supported by P-Stereogenic Linear Tetraphosphine Tetraoxide

A P-stereogenic linear tetraphosphine tetraoxide, (R,R)- or (S,S)-dpmppm(=O)₄, was synthesized to prepare C₂ dinuclear M(hfa)₃ complexes (M=Eu, Tb, Y) as the first example of lanthanide(III) complexes with P-chiral multidentate phosphine oxides. The mononuclear M(hfa)₃ complexes (M=Eu, Y) with a P-chiral diphosphine dioxide, tpdpb(=O)₂, were also prepared, and comparison of their photophysical properties for the Eu^III complexes revealed that significant chiral induction from the P-chiral centers arises on the achiral M(hfa)₃ units through intramolecular π-π stacking constraint in the dinuclear system.     

Near-IR Luminescent YbIII Coordination Polymers Composed of Pyrene Derivatives for Thermostable Oxygen Sensors

Oxygen-sensitive and near-infrared (NIR) luminescent Yb^III coordination polymers incorporating ligands based on pyrene derivatives were synthesized: Yb^III–TBAPy and Yb^III–TIAPy (TBAPy: 1,3,6,8-tetrakis(p-benzoate)pyrene; TIAPy: 1,3,6,8-tetrakis(3,5-isophthalic acid)pyrene). The coordination structures of these materials have been characterized by means of electrospray ionization mass spectrometry, X-ray diffraction analysis, and thermogravimetric analysis. Moreover, the porous structure of Yb^III–TIAPy has been evaluated by measuring its N₂ adsorption isotherm. The NIR luminescence properties of Yb^III–TBAPy and Yb^III–TIAPy have been examined by acquiring emission spectra and determining emission lifetimes under air or argon and in vacuo. Yb^III–TIAPy exhibited high thermal stability (with a decomposition temperature of 400 °C), intense luminescence (with an emission quantum yield under argon of 6.6 %), and effective oxygen-sensing characteristics. These results suggest that NIR luminescent Yb^III coordination polymers prepared using pyrene derivatives could have applications in novel thermo-stable oxygen sensors.     

Extension of the LP-Newton method to conic programming problems via semi-infinite representation

Numerical Algorithms - The LP-Newton method solves linear programming (LP) problems by repeatedly projecting a current point onto a certain relevant polytope. In this paper, we extend the...     

On Default Priors for Robust Bayesian Estimation with Divergences

This paper presents objective priors for robust Bayesian estimation against outliers based on divergences. The minimum γ-divergence estimator is well-known to work well in estimation against heavy contamination. The robust Bayesian methods by using quasi-posterior distributions based on divergences have been also proposed in recent years. In the objective Bayesian framework, the selection of default prior distributions under such quasi-posterior distributions is an important problem. In this study, we provide some properties of reference and moment matching priors under the quasi-posterior distribution based on the γ-divergence. In particular, we show that the proposed priors are approximately robust under the condition on the contamination distribution without assuming any conditions on the contamination ratio. Some simulation studies are also presented.     

Stereoselective Synthesis of the Proposed C79–C104 Fragment of Symbiodinolide

Stereoselective and streamlined synthesis of the proposed C79–C104 fragment 2 of symbiodinolide ( 1 ), a polyol marine natural product with a molecular weight of 2860, was achieved. In the synthetic route, the proposed C79–C104 fragment 2 was synthesized by utilizing a Julia–Kocienski olefination and subsequent Sharpless asymmetric dihydroxylation as key transformations in a convergent manner. Detailed comparison of the ¹³C NMR chemical shifts between the natural product and the synthetic C79–C104 fragment 2 revealed that the stereostructure at the C91–C99 carbon chain moiety of symbiodinolide ( 1 ) should be reinvestigated.