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  1. Nanostructured Catalysts
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Among them, the catalyst precursor C5 was found to be the most efficient, since decreasing the catalyst loading from 0. The discovery of new classes of hydrogenation catalysts that deviate from the Noyori-type C1 may represent a good opportunity to reduce every type of ketone substrate with high reactivity and selectivity. AH using non-phosphine-based catalysts is attractive due to the toxicity of the catalyst precursors and the product contamination when Noyori-type catalysts are used.

Interestingly, this new catalyst system catalyzes the hydrogenation of 1-indanone only in the absence of a base. The most efficient AH catalysts tend to mimic that of Noyori as its excellent enantioselectivity is proposed to be a result of the synergistic effect of chiral phosphane and chiral amine ligands. Since ketones coordinate more weakly to metals than olefins, many Rh-phosphane complexes show no activity for hydrogenation of simple ketones.

Jiang et al. The hydrogenation of ketones catalyzed by chiral iridium complexes has been well studied and developed because iridium is less expensive than rhodium Malacea et al. Xie et al. The introduction of an additional coordination group in the bidentate spiro aminophosphine ligand L6 led to a very stable and efficient catalyst for the AH of simple ketones 27, affording the chiral alcohols 28 in up to Moreover, chemo-, regio- and stereoselectivity can often be different from that of AH.

In the ATH process, the transition-metal catalyst is able to abstract a hydride and a proton from the hydrogen donor and deliver them to the carbonyl moiety of the ketone. A major drawback of using i -PrOH is the reaction reversibility, giving limited conversions and affecting the enantiomeric purity of the products after long reaction times.

The use of formic acid can overcome these drawbacks, although only a narrow range of catalysts that tolerate formic acid is available. In parallel with the discovery of efficient ruthenium catalysts for AH, Noyori and co-workers found a prototype of chiral arene Ru II catalysts of type C8 bearing N -sulfonated 1,2-diamines e.

It was first disclosed by Noyori, that a N-H moiety is necessary for an efficient transfer of hydrogen from the metal hydride. In contrast, H 2 -hydrogenation is less successful when using this system.

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There is a continuing search for stable catalysts that would not degrade easily during the hydrogenation process, thus making it possible to execute as many as possible catalytic cycles. The complexes C11 and C12 were not isolated but used in situ. In this respect the development of catalysts with similar properties to replace platinum-group metals is very desirable from both the economic and environmental points of view.

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In fact, iron is cheap and ubiquitous, and its traces in final products are not as serious a problem as traces of ruthenium, for example Morris, A range of aryl, alkyl, cyclic, heterocyclic, and aliphatic ketones were hydrogenated under 50 bar of H 2 with a combination of inexpensive Cu OAc 2 and monodentate binaphthophosphepine ligand L17 Junge et al. Owing to the stronger bonding of Os compared to Ru, robust and thermally stable complexes can be obtained, which is important for achieving highly productive catalysts. The main disadvantage, however, is the low solubility of the homogenous metal catalysts and most of the organic substrates when going from organic to aqueous media, which may be reflected in a reduced activity and selectivity.

To circumvent this, either hydrophilic, often charged, functionalities can be introduced to ligands to render the catalysts water-soluble, or different surfactants can be added in order to solvate the reaction partners, although in some cases water-insoluble catalysts can deliver a superior activity and selectivity. The latter catalyst system appeared to be quite stable, since it could be recycled six times with little loss of performance. Similarly, an in-situ -prepared catalytic complex from the proline-functionalized ligand L21 and [RuCl 2 p -cymene ] 2 in a ratio showed good activity for the aqueous ATH of acetophenone-type ketones as well as bicyclic ketones Manville et al.

The tethered Rh complex C20 reported by Wills acts as a very productive catalyst for aqueous-reduction as it continues to turnover a reaction at low loadings, even at 0. The chiral aqua Ir III -complex C21 bearing non-sulfonated diamine was shown to be very flexible in the ATH of -cyano- and -nitroacetophenones as the reaction can be conducted at pH 2 formic acid as well as at pH 5. Surfactants are often added as co-solvents to obtain a sufficient solubility of the reactants, products and metal catalysts, thus retaining the activity and selectivity of the hydrogenation process.

It is notable that catalysts embedded in these micro-reactors can be separated from the organic phase and reused for at least six times without any loss of activity and enantioselectivity. In recent years ionic liquids ILs have attracted an increasing interest because of their non-volatility, non-flammability and low toxicity. Additionally, ILs are capable of immobilizing homogenous catalysts and facilitating the recycling of catalysts. Ideally, organic products can be easily separated by extraction with a less polar solvent and the IL phase containing catalyst can be reused.

Such an immobilization of catalysts also promises to prevent the leaching of toxic metals into the organic products, which is especially desirable in the production of pharmaceutical intermediates. In contrast, the catalyst activity showed a remarkable drop with each cycle, and therefore the reaction times had to be prolonged for high conversions. Homogenous hydrogenation and transfer hydrogenation may be mechanistically closely related because both reactions involve a metal hydride species under catalytic conditions, thus sharing a multistep pathway of hydride transfer to the ketone, i.

Applied only to the transfer hydrogenation, direct hydrogen transfer Meerwein-Ponndorf-Verly reaction from the metal alkoxyide to the ketone without the involvement of metal hydrides proceeding through a six-membered transition state has also been proposed, and is typical for non-transition metals e. Noyori and co-workers proposed metal-ligand bifunctional catalysis for their Ru catalysts containing chiral phosphine-amine ligands and for arene Ru-diamine catalysts, which consequently resulted in a widely accepted mechanism to be responsible for the highly enantio-selective hydrogenation and transfer hydrogenation of prochiral ketones Noyori et al.

The actual catalysts, Ru-hydrides 31 or 34, are usually created in a basic alcoholic solution under H 2 or not at the beginning of the catalytic reaction from the Ru precursors 30 or Note that only the trans -RuH 2 31 is a very active catalyst.

Nanostructured Catalysts

This concerted process results in the formation of an alcohol product and Ru-amido species 32 or The hydride intermediate 31 or 34 is then regenerated either by the addition of molecular hydrogen or by the reverse hydrogen transfer from a dihydrogen source e.

The latter step is considered to be a rate-limiting step. The overall process is occurring outside the coordination sphere of the metal without the interacting of the ketone or alcohol with the metal center. This is known as an outer-sphere mechanism.

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It is depicted in Fig. Depending on transition-metal catalysts, an ionic mechanism has also been proposed where the proton and hydride transfer occur in separate steps Bullock, The active species in catalytic cycles, Ru-hydride 31 or 34 and Ru-amido complexes 32 or 35 , have not only been detected but also isolated in some cases Abdur-Rashid et al. The absolute configuration of the alcohol product in AH is determined in the six-membered transition state resulting from the reaction of a chiral diphosphine-diamine-RuH 2 complex with a prochiral ketone Noyori et al.

Because the enantiofaces of the ketone are differentiated on the molecular surface of the saturated RuH 2 complex, a suitable combination of the catalyst and substrate is necessary for high efficiency. The prochiral ketone e. In contrast to the outer-sphere mechanism, here the ketone and alcohol interact with the metal center. One is chirally modified supported metals, and the other is the immobilized homogeneous catalyst on a variety of organic and inorganic polymeric materials.

There are also two major reasons for preparing and studying heterogeneous catalysts: firstly, and most importantly, the better and advanced separation and handling properties, and, secondly, the potential to create catalytic positions with an improved catalytic performance. The ultimate heterogeneous catalyst can easily be renewed, reused without of loss of activity and selectivity, which are at least as good or even better than those of the homogeneous analogue.

The immobilization of a homogeneous metal coordination complex is a useful strategy in the preparation of new hydrogenation catalysts. Much effort has been devoted to the preparation of such heterogenized complexes over the past decade due to their ease of separation from the reaction mixture and the desired minimal product contamination caused by metal leaching, as well as to their efficient recyclability without any significant loss of activity. Preferably, Rh, Ir, and Ru complexes have been employed in the hydrogenations of carbonyl functionality Corma et al. Chemically different supports have been used for the immobilization of various homogeneous complexes, including polymeric organic and inorganic supports Saluzzo et al.

Supports of an inorganic nature are more suitable owing to their physical properties, chemical inertness and stability with respect to swelling and deformation in organic solvents. The above-mentioned properties of the inorganic supports will facilitate the applications of the materials in reactions carried at higher temperatures and their use in continuous-flow reactions. Immobilization via covalent bonds is undoubtedly the most convenient, but on the other hand, it is the most challenging method for immobilization to perform on such supports Jones et al.

On the other hand, polar solvents such as water or alcohols and high temperatures during the catalytic procedure can promote the hydrolysis of the grafted moieties. The heterogenized catalysts can potentially combine the advantages of both homogenous and heterogeneous systems. In , Hu and coworkers developed a novel chiral porous solid catalyst based on zirconium phosphonates for the practically useful enantio-selective hydrogenation of unfunctionalized aromatic ketones Fig.

Acetophenone was hydrogenated, producing 1-phenylethanol with a complete conversion and As indicated in table 1 , the Ru- R -C24 immobilized catalyst has also been tested to catalyze the hydrogenation of other aromatic ketones resulting in the formation of the corresponding alcohols with the same high enantioselectivity The authors believe that the modest enantioselectivities observed for the Ru- R -C25 catalyst originate in the substituent effects on the BINAP ligand.

Furthermore, the catalysts were successfully reused without any deterioration of the enantioselectivity in eight cycles.

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  • The introduced catalysts can be readily recycled and reused Hu et al. The catalysts were tested for the heterogeneous asymmetric hydrogenation of aromatic ketones showing a remarkably high activity and enantioselectivity Table 1. Liu et al. In particular, the catalyst could be recovered and reused in multiple consecutive runs up to 10 uses with a completely maintained enantioselectivity.

    Additionally, Li and coworkers J. Chiral Ru and Ir, mesoporous, silica-supported catalysts were introduced by Liu and coworkers G. The catalyst was recovered and reused several times without considerably affecting the ee values. Two magnetic chiral Ir and Rh catalysts were prepared via directly post-grafting 1,2-diphenylethylenediamine and 1,2-cyclohexanediamine-derived organic silica onto silica-coated iron oxide nanoparticles G. Both catalysts could be recovered by magnetic separation and be reused ten times without significantly affecting their catalytic activities and enantioselectivities.

    The chiral RuCl 2 -diphosphine-diamine complex with siloxy functionality was successfully immobilized on mesoporous silica nanospheres with three-dimensional channels Fig. Upon activation with t -BuOK, the catalysts CC36 can be used for the AH of aromatic ketones; however, CC36 exhibit lower enantioselectivities than their parent homogeneous catalysts. Catalysts of the type CC34 were also examined in a dynamic kinetic resolution of -branched aryl aldehydes. The saving grace is its machine learning-powered search function, which indexes the spoken content of episodes to help you find what you want.

    But while Podcasts is basic, the Apple TV app feels positively half-baked. Upon first launching it we were greeted by two rows of buttons for TV shows or films, with a huge blank space below. The app is organized by tabs at the top, which instantly breaks with the design principles of the Music and Podcasts apps, which both use a sidebar. The main screen of the TV app, meanwhile, is mostly filled with buttons for shows and movies and almost completely devoid of text explaining what each of these shows are even about. If you want to browse genres, you have to scroll all the way to the bottom of each section.

    The pages for individual shows and films are much better, with large banners, blurbs and episode lists. It feels very unfinished, like it was the app Apple devoted the least time to. With that in mind, Apple has now moved it to the Finder sidebar. It looks almost exactly the same as it did in iTunes, it just lives in a new home now. Sidecar is a new feature that lets you control a Mac using a connected iPad. This is especially promising if you have an Apple Pencil, as you will be able to draw on or mark up Mac documents using your iPad.

    It can also be configured to have the iPad work as a second display — this could be used to house a second app that you reference while you work on your Mac, for example. Connecting the two devices was a breeze, and you can do it either wirelessly or wired. The wireless option is set up through AirPlay or a specific settings menu in System Preferences. There are a few more requirements, such as making sure both devices are using the same iCloud account and are both supported devices. Once you do have the two devices paired, you can easily drag windows right over to the iPad screen, use it for your toolbars and controls, or whatever else you like to do with extra screen real estate.

    Drawing and writing on the iPad directly into MacOS feels just as smooth as it would on the iPad itself, and being able to do that in full native desktop applications is awesome. That functionality has now made it across to MacOS. You can go back to see how today compares to your usage on previous days, too.

    The sidebar contains a number of sections, including Notifications and Pickups. The old Reminders app was far too basic, but now you get features that have been standard in rival apps for a long time. Further down the sidebar are Downtime and Always Allowed, which are all about encouraging you to take a break from your Mac.

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    In Downtime you can schedule a period of time wherein only allowed apps those specified in the Always Allowed section and phone calls are permitted on your Mac you can also limit calls in the Communication section. The App Limits section, predictably, lets you set limits on how long you can use certain apps each day. You can put limits on individual apps or entire categories, such as games, social networking or entertainment.

    Each app or category can be limited to the same time every day, or you can specify different schedules for different days. We got a really good impression from Screen Time. Several core Apple apps have been updated in Catalina, with the extent of the updates varying by app. Notes, for example, got a minor bump with a new gallery view that shows your notes as thumbnails rather than a list. It also now supports shared folders. Apple lets you view your photos by day, month or year, with highlights automatically selected by the app. Meanwhile, Reminders has been completely redesigned to bring it up to date.

    Unfortunately, this is a little uneven. Still, the Reminders redesign is an improvement over its lackluster predecessor. Most of the software focus is on iOS, and there was very little in the way of new ways to interact with your Mac. Sidecar, on the other hand, feels substantial. Our first impressions of these new apps has not been the most positive, so hopefully Apple can continue working on them before the official launch in the Fall.

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