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Upstream product

• 1499-21-4 Diphenylphosphinic chloride 
• 31327-19-2 1-phenylvinyl diphenylphosphinate 
• 98-86-2 acetophenone 

Downstream Products

• 2516-22-5 1-(2-(1-phenylethoxy)ethyl)benzene 
• 2040-37-1 benzyl 1-phenylethyl ether 
• 61812-55-3 (1-cyclohexyloxy-ethyl)-benzene 
• 1445-91-6 (S)-1-phenylethanol 
• 1517-69-7 (R)-1-phenylethanol 

Relevant academic research and scientific papers

Indene Derived Phosphorus-Thioether Ligands for the Ir-Catalyzed Asymmetric Hydrogenation of Olefins with Diverse Substitution Patterns and Different Functional Groups

A family of phosphite/phosphinite-thioether ligands have been tested in the Ir-catalyzed asymmetric hydrogenation of a range of olefins (50 substrates in total). The presented ligands are synthesized in three steps from cheap indene and they are air-stable solids. Their modular architecture has been crucial to maximize the catalytic performance for each type of substrate. Improving most Ir-catalysts reported so far, this ligand family presents a broader substrate scope, covering different substitution patterns with different functional groups, ranging from unfunctionalized olefins, through olefins with poorly coordinative groups, to olefins with coordinative functional groups. α,β-Unsaturated acyclic and cyclic esters, ketones and amides werehydrogenated in enantioselectivities ranging from 83 to 99% ee. Enantioselectivities ranging from 91 to 98% ee were also achieved for challenging substrates such as unfunctionalized 1,1′-disubstituted olefins, functionalized tri- and 1,1′-disubstituted vinyl phosphonates, and β-cyclic enamides. The catalytic performance of the Ir-ligand assemblies was maintained when the environmentally benign 1,2-propylene carbonate was used as solvent. (Figure presented.).

Density Functional Theory-Inspired Design of Ir/P,S-Catalysts for Asymmetric Hydrogenation of Olefins

In silico-based optimization of Ir/P,S-catalysts for the asymmetric hydrogenation of unfunctionalized olefins using (E)-1-(but-2-en-2-yl)-4-methoxybenzene as a benchmark olefin has been carried out. DFT calculations revealed that the thioether group has a major role in directing the olefin coordination. This, together with the configuration of the biphenyl phosphite group, has an impact in maximizing the energy gap between the most stable transition states leading to opposite enantiomers. As a result, the optimized catalyst proved to be efficient in the hydrogenation of a range of alkenes with the same substitution pattern and olefin geometry as the benchmark olefin, regardless of the presence of functional groups with different coordination abilities (ee values up to 97%). Appealingly, further modifications at the thioether groups and at the biaryl phosphite moiety allowed the highly enantioselective hydrogenation of olefins with different substitution patterns (e.g., α,β-unsaturated lactones and lactams, 1,1′-disubstituted enol phosphinates, and cyclic β-enamides; ee values up to >99%).

Ir/Thioether-Carbene, -Phosphinite, and -Phosphite Complexes for Asymmetric Hydrogenation. A Case for Comparison

We studied for the first time the potential of novel and simple Ir/thioether-NHC complexes in the asymmetric hydrogenation of unfunctionalized olefins and cyclic β-enamides. For comparison, we prepared and applied the analogues thioether-phosphinite/phosphite complexes. We found that the efficiency of the new Ir/thioether-NHC catalyst precursors varies with the type of olefin. Thus, while the Ir/thioether-NHC catalyst precursors provided lower catalytic performance than their related Ir/thioether-P complexes in the hydrogenation of olefins lacking a coordinating group, the catalysts had similar good performance for the reduction of functionalized olefins (e.g., tri- and disubstituted enol phosphonate derivatives). Catalytic results together with the studies of the reactivity toward H2 indicated that the thioether-carbene design favors the formation of inactive trinuclear species, which are responsible for the low activities obtained with these carbene-type catalysts. Nevertheless, this catalyst deactivation can be avoided by using functionalized olefins such as enol phosphonates. We also report the discovery of simple-to-synthesize Ir/thioether-P catalysts containing a simple backbone that gave high enantioselectivities for some trisubstituted olefins, some challenging 1,1′-disubstituted olefins, and cyclic β-enamides.

Asymmetric Hydrogenation of Disubstituted, Trisubstituted, and Tetrasubstituted Minimally Functionalized Olefins and Cyclic β-Enamides with Easily Accessible Ir-P,Oxazoline Catalysts

We have developed a family of Ir-P,oxazoline catalysts for asymmetric hydrogenation. These catalysts, with a simple modular architecture, have shown a high tolerance to the olefin geometry and substitution pattern, and to the presence of several neighboring polar groups. Thus, they were able to successfully hydrogenate disubstituted, trisubstituted, and tetrasubstituted minimally functionalized olefins (with enantiomeric excess values up to 99%). The excellent catalytic performance was also extended to the hydrogenation of cyclic β-enamides.

Alternatives to Phosphinooxazoline (t-BuPHOX) Ligands in the Metal-Catalyzed Hydrogenation of Minimally Functionalized Olefins and Cyclic β-Enamides

This study presents a new series of readily accessible iridium- and rhodium-phosphite/oxazoline catalytic systems that can efficiently hydrogenate, for the first time, both minimally functionalized olefins and functionalized olefins (62 examples in total) in high enantioselectivities (ees up to >99%) and conversions. The phosphite-oxazoline ligands, which are readily available in only two synthetic steps, are derived from previous privileged 4-alkyl-2-[2-(diphenylphosphino)phenyl]-2-oxazoline (PHOX) ligands by replacing the phosphine moiety by a biaryl phosphite group and/or the introduction of a methylene spacer between the oxazoline and the phenyl ring. The modular design of the ligands has given us the opportunity not only to overcome the limitations of the iridium-PHOX catalytic systems in the hydrogenation of minimally functionalized Z-olefins and 1,1-disubstituted olefins, but also to expand their use to unfunctionalized olefins containing other challenging scaffolds (e.g., exocyclic benzofused and triaryl-substituted olefins) and also to olefins with poorly coordinative groups (e.g., α,β-unsaturated lactams, lactones, alkenylboronic esters, etc.) with enantioselectivities typically >95% ee. Moreover, both enantiomers of the hydrogenation product could be obtained by simply changing the configuration of the biaryl phosphite moiety. Remarkably, the new catalytic systems also provided excellent enantioselectivities (up to 99% ee) in the asymmetric hydrogenation of another challenging class of olefins – the functionalized cyclic β-enamides. Again, both enantiomers of the reduced amides could be obtained by changing the metal from Ir to Rh. We also demonstrated that environmentally friendly propylene carbonate can be used with no loss of enantioselectivity. Another advantage of the new ligands over the PHOX ligands is that the best ligands are derived from the affordable (S)-phenylglycinol rather than from the expensive (S)-tert-leucinol. (Figure presented.).

Chiral ferrocene-based P,S ligands for Ir-catalyzed hydrogenation of minimally functionalized olefins. Scope and limitations

A family of 12 modular ferrocenyl planar chiral phosphine-thioethers (P,S) has been studied in the asymmetric hydrogenation of minimally functionalized alkenes. These ligands differ by the substituent on sulfur or by the linker between the ferrocene moiety and the sulfur atom (no linker, methylene or methyl substituted methylene linker bearing an additional element of chirality). The cationic iridium(cod) complexes of the different P,S ligands have been efficiently synthesized. For the majority of the ligands, coordination yielded only a single diastereoisomer with full control of the absolute configuration on sulfur. The different iridium complexes have been used in the hydrogenation of various di, tri, and tetrasubstituted minimally functionalized olefins. Conversions and enantioselectivities are highly dependent on the ligand and substrate structure. Full conversions and low-to-excellent enantioselectivities could be obtained (maximum ee from 14 to 94% for 1,1-disubsituted alkenes, from 17 to 99% for trisubstituted olefins, and 34% for the tetrasubstituted alkene).

Extending the substrate scope of bicyclic p-oxazoline/thiazole ligands for ir-catalyzed hydrogenation of unfunctionalized olefins by introducing a biaryl phosphoroamidite group

This study identifies a series of Ir-bicyclic phosphoroamidite-oxazoline/thiazole catalytic systems that can hydrogenate a wide range of minimally functionalized olefins (including E- and Z-tri- and disubstituted substrates, vinylsilanes, enol phosphinates, tri- and disubstituted alkenylboronic esters, and ?±,?2-unsaturated enones) in high enantioselectivities (ee values up to 99%) and conversions. The design of the new phosphoroamidite-oxazoline/thiazole ligands derives from a previous successful generation of bicyclic N-phosphane-oxazoline/thiazole ligands, by replacing the N-phosphane group with a p-acceptor biaryl phosphoroamidite moiety. A small but structurally important family of Ir-phosphoroamidite-oxazoline/thiazole precatalysts has thus been synthesized by changing the nature of the Ndonor group (either oxazoline or thiazole) and the configuration at the biaryl phosphoroamidite moiety. The substitution of the N-phosphane by a phosphoroamidite group in the bicyclic N-phosphane-oxazoline/thiazole ligands extended the range of olefins that can be successfully hydrogenated.

Asymmetric hydrogenation and allylic substitution reaction with novel chiral pinene-derived N,P-ligands

A series of new chiral tetrahydroquinoline ligands, derived from chiral α-pinene, were successfully synthesized. Iridium and palladium complexes of these ligands were proven to be efficient catalysts for enantioselective hydrogenation and allylic substitution reactions with moderate to excellent enantioselectivities (90-95% ee) and high yields.

ASYMMETRIC HYDROGENATION OF ENOL PHOSPHINATES CATALYZED BY A CHIRAL FERROCENYLPHOSPHINE- RHODIUM COMPLEX. ASYMMETRIC SYNTHESIS OF OPTICALLY ACTIVE SECONDARY ALKYL ALCOHOLS

Catalytic asymmetric synthesis of secondary alkyl alcohols (up to 78 percent ee) was accomplished by asymmetric hydrogenation of enol diphenylphosphinates, derived from prochiral ketones such as acetophenone, 3-methyl-2-butanone, and 2-octanone, in the presence of a cationic rhodium complex of (R)-1-ethanol (BPPFOH).