Decomposed Multilateral Filtering for Accelerating Filtering with Multiple Guidance Images.

This paper proposes an efficient algorithm for edge-preserving filtering with multiple guidance images, so-called multilateral filtering. Multimodal signal processing for sensor fusion is increasingly important in image sensing. Edge-preserving filtering is available for various sensor fusion applications, such as estimating scene properties and refining inverse-rendered images. The main application is joint edge-preserving filtering, which can preferably reflect the edge information of a guidance image from an additional sensor. The drawback of edge-preserving filtering lies in its long computational time; thus, many acceleration methods have been proposed. However, most accelerated filtering cannot handle multiple guidance information well, although the multiple guidance information provides us with various benefits. Therefore, we extend the efficient edge-preserving filters so that they can use additional multiple guidance images. Our algorithm, named decomposes multilateral filtering (DMF), can extend the efficient filtering methods to the multilateral filtering method, which decomposes the filter into a set of constant-time filtering. Experimental results show that our algorithm performs efficiently and is sufficient for various applications.

Suzuki-Miyaura Cross-Coupling Reaction Using Palladium Catalysts Supported on Phosphine Periodic Mesoporous Organosilica.

Phosphine periodic mesoporous organosilicas (R-P-PMO-TMS: R=Ph, tBu), which possess electron-donating alkyl substituents on the phosphorus atom, were synthesized using bifunctional compounds with alkoxysilyl- and phosphino groups, bis[3-(triethoxysilyl)propyl]phenylphosphine borane (1 a) and bis[3-(triethoxysilyl)propyl]-tert-butylphosphine borane (1 b). Immobilization of Pd(0) species was performed to give R-P-Pd-PMO-TMS: R=Ph (2 a), tBu (3 a), respectively. The Pd(0) immobilized 2 a and 3 a were applicable as catalysts for Suzuki-Miyaura cross-coupling reactions of aryl chlorides with phenylboronic acid. It was revealed that 3 a bearing more electron-donating tBu groups exhibited higher catalytic activity. Various functional groups including both electron withdrawing and donating substituents were compatible in the system. The recyclability of 3 a was examined to support its moderate utility for the recycle use.

Borane-Protecting Strategy for Hydrosilylation of Phosphorus-Containing Olefins.

Ir-catalyzed hydrosilylation of the alkenyl phosphine borane complex 1 was achieved to give the corresponding products 2. Because the phosphino group coordinates with metals and is unstable under aerobic conditions, the formation of the corresponding borane adduct was effective not only to promote the target hydrosilylation but also to keep 1 stable under aerobic conditions. The removal of coordinated borane from 2 was readily performed with the treatment by 1,4-diazabicyclo[2.2.2]octane to apply to further transformations. The immobilization and following deprotection of 2 on the surface of mesoporous silica were also examined.

One-Pot Synthesis of Polymers Containing PC Bonds in the Main Chain.

Placement of phosphorus in the polymer main chain leads to organophosphorus polymers with potentially unique chemical and physical properties. Herein, it is demonstrated that the Abramov phosphonylation reaction can be extended to the synthesis of such polymers, by reacting di- or tricarbaldehydes with phosphinic acid (PA) in the presence of N,O-bis(trimethylsilyl)acetamide (BSA). This technique affords polymers with main chain PC bonds, wherein phosphorus (V), aromatic rings, and hydroxymethylene moieties are linked by bis(α-hydroxymethylene)phosphinic acid (BHMPA) units. The resulting polymers are water soluble, display resilience against acid- and base-catalyzed hydrolysis, and exhibit superior thermal stability with high char yield in air (≈83%) and nitrogen (≈76%) atmosphere.

A General and Selective Synthesis of Methylmonochlorosilanes from Di-, Tri-, and Tetrachlorosilanes.

Direct catalytic transformation of chlorosilanes into organosilicon compounds remains challenging due to difficulty in cleaving the strong Si-Cl bond(s). We herein report the palladium-catalyzed cross-coupling reaction of chlorosilanes with organoaluminum reagents. A combination of [Pd(C3H5)Cl]2 and DavePhos ligand catalyzed the selective methylation of various dichlorosilanes 1, trichlorosilanes 5, and tetrachlorosilane 6 to give the corresponding monochlorosilanes.

Selective hydrosilylation of allyl chloride with trichlorosilane.

The transition-metal-catalysed hydrosilylation reaction of alkenes is one of the most important catalytic reactions in the silicon industry. In this field, intensive studies have been thus far performed in the development of base-metal catalysts due to increased emphasis on environmental sustainability. However, one big drawback remains to be overcome in this field: the limited functional group compatibility of the currently available Pt hydrosilylation catalysts in the silicon industry. This is a serious issue in the production of trichloro(3-chloropropyl)silane, which is industrially synthesized on the order of several thousand tons per year as a key intermediate to access various silane coupling agents. In the present study, an efficient hydrosilylation reaction of allyl chloride with trichlorosilane is achieved using the Rh(I) catalyst [RhCl(dppbzF)]2 (dppbzF = 1,2-bis(diphenylphosphino)-3,4,5,6-tetrafluorobenzene) to selectively form trichloro(3-chloropropyl)silane. The catalyst enables drastically improved efficiency (turnover number, TON, 140,000) and selectivity (>99%) to be achieved compared to conventional Pt catalysts.

Selective C-P(O) Bond Cleavage of Organophosphine Oxides by Sodium.

Sodium exhibits better efficacy and selectivity than Li and K for converting Ph3P(O) to Ph2P(OM). The destiny of PhNa co-generated is disclosed. A series of alkyl halides R4X and aryl halides ArX all react with Ph2P(ONa) to produce the corresponding phosphine oxides in good to excellent yields.

Co(I) complexes with a tetradentate phenanthroline-based PNNP ligand as a potent new metal-ligand cooperation platform.

A series of low spin cobalt(i) complexes bearing a tetradentate phenanthroline-based PNNP ligand (2,9-bis((diphenylphosphanyl)methyl)-1,10-phenanthroline), [CoCl(PNNP)] (1), [CoMe(PNNP)] (2) and [Co(CH2SiMe3)(PNNP)] (3), were synthesized and structurally identified. Complex 3 underwent a structural rearrangement of the PNNP skeleton upon heating to form [Co(PNNP')] (4), which is supported by an asymmetrical PNNP' ligand with a dearomatized phenanthroline backbone. Mechanistic studies supported that the transformation from 3 to 4 was initiated by the homolysis of either a Co-CH2SiMe3 bond or a benzylic C-H bond. Complex 4 achieved H-H bond cleavage of H2 (1 atm) at ambient temperature, to form [Co(PNNP'')] (6), in which two H atoms were incorporated into the endocyclic double bond of the PNNP'' ligand backbone.

Polypropylene-Based Nanocomposite with Enhanced Aging Stability by Surface Grafting of Silica Nanofillers with a Silane Coupling Agent Containing an Antioxidant.

Simultaneous improvement in the mechanical properties and lifetime of polymer nanocomposites is crucially significant to further extend the versatility of polymer materials and reduce environmental impact. In this study, we fabricated reinforced polypropylene (PP)-based nanocomposites with improved aging stability by the addition of surface-modified well-ordered silica nanospheres with a silane coupling agent (SCA) containing hindered phenol antioxidant as a filler. Uniform grafting of the SCA on the filler surface contributed to homogeneous dispersion of the filler into the matrix, leading to improved properties (e.g., stiffness and ductility) and uniform distribution of the antioxidant component into the entire nanocomposite by filler dispersion. The grafting of SCA also likely provides an inhibitory effect on antioxidant migration, which leads to loss of polymer stability during the aging process. This novel idea for the material design of PP-based nanocomposites, which simultaneously enhances their mechanical properties and lifetime, is promising for application in the fabrication of various types of polymer nanocomposites.

Heterogeneous hydrosilylation reaction catalysed by platinum complexes immobilized on bipyridine-periodic mesoporous organosilicas.

The utility of a bipyridine periodic mesoporous organosilica, BPy-PMO, as a support material of a hydrosilylation catalyst was investigated in the hydrosilylation of phenylacetylene with trimethoxysilane. [PtMe2(BPy-PMO)] (1) exhibited a moderate catalytic activity, whereas the reaction was successfully catalysed by [PtMe2(BPy-PMO-TMS)] (2) bearing end-capped TMS groups on the surface. Spectroscopic analyses of 2 revealed that the porous structure of BPy-PMO-TMS remained almost unchanged through the reaction. The hot filtration test supported the nonleaching property of 2, thereby exhibiting good reusability without the loss of the product yields.

Structural exploration of rhodium catalysts and their kinetic studies for efficient parahydrogen-induced polarization by side arm hydrogenation.

Parahydrogen-induced polarization (PHIP) is a rapid and cost-effective hyperpolarization technique using transition metal-catalysed hydrogenation with parahydrogen. We examined rhodium catalysts and their kinetic studies, rarely considered in the research of current PHIP. It emerged that rhodium complexes with electron-donating bisphosphine ligands, with a dicyclohexylphosphino group, appear to be more effective than conventional rhodium catalysts.

Direct Silyl-Heck Reaction of Chlorosilanes.

A nickel complex/Lewis acid combination effectively catalyzed the direct silyl-Heck reaction of chlorosilanes, which are key raw materials in the organosilicon industry, to give synthetically important alkenylsilane products. Trichlorosilanes, dichlorosilanes, and monochlorosilanes underwent the silyl-Heck reaction to afford the corresponding alkenylsilanes in high yields. In the reactions of dichlorosilanes, a single substitution occurred to give monoalkenylsilanes in a highly selective manner.

Design of bifunctional chiral phenanthroline ligand with Lewis basic site for palladium-catalyzed asymmetric allylic substitution.

Conceptually new bifunctional chiral ligands were developed. The axially chiral N,N-bidentate phenanthroline ligand (S)-1 was found to be effective for Pd-catalyzed asymmetric allylic substitution of allyl acetate and dialkyl malonate. The intramolecular Lewis basic group from the hydroxybinaphthyl structure of (S)-1 played a pivotal role in the high reactivity and enantioselectivity.

Renovation of Optically Active Phenanthrolines as Powerful Chiral Ligands for Versatile Asymmetric Metal Catalysis.

In the field of asymmetric synthesis, the development of new chiral ligands has been regarded as an attractive challenge for decades. Novel chiral ligands can often have a great impact on synthetic protocols. In this context, we are currently interested in the application of 1,10-phenanthroline (phen) as an entirely new class of chiral ligand. To handle this issue, we designed a chiral phen ligand that provides the N,N,O-tridentate coordination of the phen moiety and an additional phenolic hydroxyl group. As phen possesses greater coordination ability with various ions, our chiral phen ligand would be valuable as one of the "privileged" chiral ligands applied to a broad range of metal catalysts and new reactions. This account summarizes the results of the application of the chiral phen ligand to various kinds of metal catalysis.

Asymmetric Induction at Remote Quaternary Centers of Cyclohexadienones by Rhodium-Catalyzed Conjugate Hydrosilylation.

The enantioselective desymmetrizing conjugate hydrosilylation of prochiral differently γ,γ-disubstituted cyclohexadienone derivatives 2 to furnish the corresponding cyclohexenones 4 with a remote chiral all-carbon quaternary center at the γ position is described. Chiral rhodium-bis(oxazolinyl)phenyl complexes 1 were effective catalysts for this transformation. This catalytic system was extended to the asymmetric transformation of spirocarbocyclic cyclohexadienones 5 to give the corresponding products 6 with high enantiomeric ratios.

Cu(ii)-catalyzed enantioselective oxygen atom transfer from oxaziridine to oxindole derivatives with chiral phenanthroline.

In the presence of a Cu(ii) complex of axially chiral, N,N,O-tridentate phenanthroline ligand (S)-2, asymmetric oxygen atom transfer of oxindole derivatives (3) using Davis' oxaziridine (4) occurred to give the corresponding 3-aryl-3-hydroxy-2-oxindole derivatives (1) with excellent enantioselectivity (up to 96% ee). The X-ray crystallographic analysis of the isolated Cu(ii) complex disclosed its N,N,O-tridentate coordination, which is critical to realize effective catalytic activity.

Construction of a Chiral Silicon Center by Rhodium-Catalyzed Enantioselective Intramolecular Hydrosilylation.

Rhodium-catalyzed enantioselective desymmetrizing intramolecular hydrosilylation of symmetrically disubstituted hydrosilanes is described. The original axially chiral phenanthroline ligand (S)-BinThro (Binol-derived phenanthroline) was found to work as an effective chiral catalyst for this transformation. A chiral silicon stereogenic center is one of the chiral motifs gaining much attention in asymmetric syntheses and the present protocol provides cyclic five-membered organosilanes incorporating chiral silicon centers with high enantioselectivities (up to 91 % ee). The putative active Rh(I) catalyst takes the form of an N,N,O-tridentate coordination complex, as determined by several complementary experiments.

Design of novel chiral N,N,O-tridentate phenanthroline ligands and their application to enantioselective addition of organozinc reagents to aldehydes.

The novel N,N,O-tridentate phenanthroline ligand (BinThro) bearing an axially chiral binaphthyl backbone prepared from BINOL was found to be an effective chiral catalyst for enantioselective addition of diethylzinc to aromatic aldehydes with high enantioselectivity (up to 95% ee).

Desymmetrizing asymmetric ring expansion of cyclohexanones with α-diazoacetates catalyzed by chiral aluminum Lewis acid.

Chiral aluminum Lewis acid catalyst composed of Me(3)Al and 3,3'-bis(trimethylsilyl)-BINOL in a 2:1 ratio was found to promote novel catalytic asymmetric ring expansion of cyclohexanone with α-substituted α-diazoacetates to give seven-membered rings with an all-carbon quaternary center. Application of this strategy to 4-substituted cyclohexanones opened up a novel way for the catalytic desymmetrizing asymmetric construction of cycloheptanones bearing remote α,δ-chiral centers.

Desymmetrizing asymmetric ring expansion: stereoselective synthesis of 7-membered cyclic beta-keto carbonyl compounds with an alpha-hydrogen.

Ring expansion of symmetrically substituted cyclohexanones with N-alpha-diazoacetyl camphorsultam was devised as a stereoselective pathway to the functionalized 7-membered cyclic beta-keto carbonyls having a kinetically stabilized alpha-hydrogen.