Forging a Cage into a Chain: Stepwise Transformation of P4_4 by Silylenes to a Si3_3P4_4 Motif

We have discovered a route to access the longest low-valent molecular silaphospha-chain, a seven-membered chain structure that incorporates three silicon and four phosphorus atoms by stepwise activation of white phosphorus (P$_4$) using two different silylene precursors. The chain species was formed via a highly reactive polyphosphide intermediate. The isolation of a stable analogue of this reaction intermediate was achieved by stepwise reaction with mono and bis(silylenes). Due to the rigidity of the ferrocenediyl framework of the bis(silylene), the isomerization process of the chain structure was hampered. Theoretical studies such as natural bond orbital and atoms in molecules analyses of the seven-membered chain species indicated some degree of delocalization of the double bond system

Enantioselective synthesis of gem-disubstituted N-Boc diazaheterocycles via decarboxylative asymmetric allylic alkylation

An enantioselective synthesis of diverse N4-Boc-protected α,α-disubstituted piperazin-2-ones using the palladium-catalyzed decarboxylative allylic alkylation reaction has been achieved. Using a chiral Pd-catalyst derived from an electron deficient PHOX ligand, chiral piperazinones are synthesized in high yields and enantioselectivity. The chiral piperazinone products can be deprotected and reduced to valuable gem-disubstituted piperazines. This reaction is further extended to enable the enantioselective synthesis of α,α-disubstituted tetrahydropyrimidin-2-ones, which are hydrolyzed into corresponding chiral β^(2,2)-amino acids

Palladium-Catalyzed Decarboxylative Asymmetric Allylic Alkylation of 1,4-Diazepan-5-ones

We report the palladium-catalyzed asymmetric allylic alkylation of 1,4-diazepan-5-ones. This reaction proceeds smoothly to give gem-disubstituted diazepanone heterocycles bearing various functional groups in up to >99% yield and up to 95% ee. An electron-rich p-anisoyl lactam protecting group and the use of a nonpolar solvent proved crucial to obtaining high enantioselectivity in most cases. Additionally, we demonstrate the use of our methodology in the synthesis of a gem-disubstituted analogue of the FDA-approved anti-insomnia drug suvorexant

Stable bidentate silylene adducts of alkaline‐earth amides

The coordination chemistry of silylenes is known for a vast number of elements of all blocks of the periodic table. However, only a handful of examples of silylene complexes have been reported for heavy alkaline-earth elements, which is mainly attributed to the “hard-soft” mismatch between the “hard” metal center and the “soft” silicon donor. Herein, we report the synthesis and characterization of a series of alkaline-earth silylene complexes comprising a bidentate pyridyl-amido-silylene ligand. The isolated Ca, Sr and Ba complexes show considerably increased stability in comparison to other known alkaline-earth silylene complexes. The molecular structures of all three complexes are essentially similar. Interestingly, depending on the central metal, the 1H NMR chemical shifts of the ortho-H atom show unexpected large differences. DFT computations were conducted to elucidate this trend in the NMR resonances

Stereoselective Activation of Small Molecules by a Stable Chiral Silene

The reaction of the dilithium salt of the enantiopure (S)-BINOL (1,1’-bi-2-naphthol) with two equivalents of the amidinate-stabilized chlorosilylene [L$^{Ph}$SiCl] (L$^{Ph}$=PhC(NtBu)$_2$) led to the formation of the first example of a chiral cyclic silene species comprising an (S)-BINOL ligand. The reactivity of the Si=C bond was investigated by reaction with elemental sulfur, CO$_2$ and HCl. The reaction with S$_8$ led to a Si=C bond cleavage and concomitantly to a ring-opened product with imine and silanethione functional groups. The reaction with CO2 resulted in the cleavage of the CO$_2$ molecule into a carbonyl group and an isolated O atom, while a new stereocenter is formed in a highly selective manner. According to DFT calculations, the [2+2] cycloaddition product is the key intermediate. Further reactivity studies of the chiral cyclic silene with HCl resulted in a stereoselective addition to the Si=C bond, while the fully selective formation of two stereocenters was achieved. The quantitative stereoselective addition of CO$_2$ and HCl to a Si=C bond is unprecedented

Differential processing of binocular and monocular gloss cues in human visual cortex.

The visual impression of an object's surface reflectance ("gloss") relies on a range of visual cues, both monocular and binocular. Whereas previous imaging work has identified processing within ventral visual areas as important for monocular cues, little is known about cortical areas involved in processing binocular cues. Here, we used human functional MRI (fMRI) to test for brain areas selectively involved in the processing of binocular cues. We manipulated stereoscopic information to create four conditions that differed in their disparity structure and in the impression of surface gloss that they evoked. We performed multivoxel pattern analysis to find areas whose fMRI responses allow classes of stimuli to be distinguished based on their depth structure vs. material appearance. We show that higher dorsal areas play a role in processing binocular gloss information, in addition to known ventral areas involved in material processing, with ventral area lateral occipital responding to both object shape and surface material properties. Moreover, we tested for similarities between the representation of gloss from binocular cues and monocular cues. Specifically, we tested for transfer in the decoding performance of an algorithm trained on glossy vs. matte objects defined by either binocular or by monocular cues. We found transfer effects from monocular to binocular cues in dorsal visual area V3B/kinetic occipital (KO), suggesting a shared representation of the two cues in this area. These results indicate the involvement of mid- to high-level visual circuitry in the estimation of surface material properties, with V3B/KO potentially playing a role in integrating monocular and binocular cues.This project was supported by fellowships to A.E.W. from the Wellcome Trust (095183/Z/10/Z) and to H.B. from the Japan Society for the Promotion of Science (JSPS KAKENHI (26870911)).This is the final version of the article. It first appeared from the American Physiological Society via https://doi.org/10.1152/jn.00829.201

Indications for Factorization and ReVub<0Re V_{ub} < 0 from Rare B Decay Data

Surveying known hadronic rare B decays, we find that the factorization approximation can give a coherent account of $K\pi$, $\pi\pi$ and $\rho^0\pi^+$ data and give predictions for $\omega^0\pi^+$, $\rho\pi$ and $K^*\pi$ modes, {\it if ${Re}V_{ub}$ is taken as negative} (in standard phase convention) rather than positive. As further confirmation, we expect a lower $\sin2\beta$ value at B Factories as compared to current fits, and $B_s$ mixing close to LEP bounds at SLD and CDF.Comment: 11 pages, revtex, 4 figures (unchanged and eps files included); version (including title and abstract change) to appear in Phys. Rev. Let

Enantioselective synthesis of gem-disubstituted N-Boc diazaheterocycles via decarboxylative asymmetric allylic alkylation

An enantioselective synthesis of diverse N4-Boc-protected α,α-disubstituted piperazin-2-ones using the palladium-catalyzed decarboxylative allylic alkylation reaction has been achieved. Using a chiral Pd-catalyst derived from an electron deficient PHOX ligand, chiral piperazinones are synthesized in high yields and enantioselectivity. The chiral piperazinone products can be deprotected and reduced to valuable gem-disubstituted piperazines. This reaction is further extended to enable the enantioselective synthesis of α,α-disubstituted tetrahydropyrimidin-2-ones, which are hydrolyzed into corresponding chiral β^(2,2)-amino acids