34857-28-8

Usage

Chemical Properties

Colorless liquid

InChI:InChI=1/C10H14O/c1-8(2)10(11)9-6-4-3-5-7-9/h3-8,10-11H,1-2H3/t10-/m0/s1

Upstream product

• 768-49-0 (2-methyl-1-propenyl)-benzene 
• 557-20-0 diethylzinc 
• 100-52-7 benzaldehyde 
• 920-39-8 isopropylmagnesium bromide 
• 81978-46-3 (1R,2S,4S,6S,7R)-1,10,10-Trimethyl-4-(2-methyl-1-phenyl-propoxy)-3-oxa-tricyclo[5.2.1.0^2,6]decane 
• 611-70-1 phenyl isopropyl ketone 
• 538-93-2 1-phenyl-2-methylpropane 
• 1078-58-6 diphenylzinc 
• 78-84-2 isobutyraldehyde 
• 611-69-8 rac-2-methyl-1-phenylpropan-1-ol 
• 108-24-7 acetic anhydride 
• 93-97-0 benzoic acid anhydride 
• 123-62-6 propionic acid anhydride 
• 91900-70-8 (+/-)-2-methyl-1-phenylprop-1-yl hydroperoxide 

Downstream Products

• 62039-13-8 (S)-1-cyclohexyl-2-methylpropan-1-ol 
• 136476-05-6 (E)-2-Methyl-3-((S)-2-methyl-1-phenyl-propoxy)-propenal 
• 106968-19-8 (S)-2 
• 128864-59-5 (R)-Fluoro-phenyl-acetic acid (S)-2-methyl-1-phenyl-propyl ester 
• 171334-35-3 (R)-(4-Chloro-phenyl)-fluoro-acetic acid (S)-2-methyl-1-phenyl-propyl ester 
• 106968-30-3 3,3,3-Trifluoro-2-methoxy-2-phenyl-propionic acid 2-methyl-1-phenyl-propyl ester 
• 108167-52-8 ((S)-2-Methyl-1-pent-1-ynyloxy-propyl)-benzene 
• 69910-23-2 (E)-3-Phenyl-but-2-enoic acid (S)-2-methyl-1-phenyl-propyl ester 
• 182691-23-2 (S)-carbonic acid 2-methyl-1-phenylpropyl ester 4-nitrophenyl ester 
• 176435-87-3 (R)-3-(2-Fluoro-phenyl)-2-methyl-2-((S)-2-methyl-1-phenyl-propoxycarbonylamino)-propionic acid 
• 176436-01-4 (R)-2-Methyl-2-((S)-2-methyl-1-phenyl-propoxycarbonylamino)-3-phenyl-propionic acid 
• 176435-99-7 (R)-2-Methyl-2-((S)-2-methyl-1-phenyl-propoxycarbonylamino)-3-phenyl-propionic acid methyl ester 
• 176435-84-0 (R)-3-(2-Fluoro-phenyl)-2-methyl-2-((S)-2-methyl-1-phenyl-propoxycarbonylamino)-propionic acid methyl ester 
• 176435-88-4 (R)-3-(2,3-Difluoro-phenyl)-2-methyl-2-((S)-2-methyl-1-phenyl-propoxycarbonylamino)-propionic acid 

Relevant academic research and scientific papers

Alkylmetal Asymmetric Reduction. 10. Reaction of β-Branched Alkylaluminum Halides with Isopropyl Phenyl Ketone

The reaction of isobutylaluminum halides with isopropyl phenyl ketone has been studied in diethyl ether at 0 deg C.It has been shown that the diisobutylaluminum halides rapidly reduce the ketone to the corresponding carbinol, while the sesquihalides and t

Visible-Light-Driven Catalytic Deracemization of Secondary Alcohols

Deracemization of racemic chiral compounds is an attractive approach in asymmetric synthesis, but its development has been hindered by energetic and kinetic challenges. Here we describe a catalytic deracemization method for secondary benzylic alcohols which are important synthetic intermediates and end products for many industries. Driven by visible light only, this method is based on sequential photochemical dehydrogenation followed by enantioselective thermal hydrogenation. The combination of a heterogeneous dehydrogenation photocatalyst and a chiral molecular hydrogenation catalyst is essential to ensure two distinct pathways for the forward and reverse reactions. These reactions convert a large number of racemic aryl alkyl alcohols into their enantiomerically enriched forms in good yields and enantioselectivities.

Dynamic Kinetic Resolution of Alcohols by Enantioselective Silylation Enabled by Two Orthogonal Transition-Metal Catalysts

A nonenzymatic dynamic kinetic resolution of acyclic and cyclic benzylic alcohols is reported. The approach merges rapid transition-metal-catalyzed alcohol racemization and enantioselective Cu-H-catalyzed dehydrogenative Si-O coupling of alcohols and hydrosilanes. The catalytic processes are orthogonal, and the racemization catalyst does not promote any background reactions such as the racemization of the silyl ether and its unselective formation. Often-used ruthenium half-sandwich complexes are not suitable but a bifunctional ruthenium pincer complex perfectly fulfills this purpose. By this, enantioselective silylation of racemic alcohol mixtures is achieved in high yields and with good levels of enantioselection.

Amino Acid-Functionalized Metal-Organic Frameworks for Asymmetric Base–Metal Catalysis

We report a strategy to develop heterogeneous single-site enantioselective catalysts based on naturally occurring amino acids and earth-abundant metals for eco-friendly asymmetric catalysis. The grafting of amino acids within the pores of a metal-organic framework (MOF), followed by post-synthetic metalation with iron precursor, affords highly active and enantioselective (>99 % ee for 10 examples) catalysts for hydrosilylation and hydroboration of carbonyl compounds. Impressively, the MOF-Fe catalyst displayed high turnover numbers of up to 10 000 and was recycled and reused more than 15 times without diminishing the enantioselectivity. MOF-Fe displayed much higher activity and enantioselectivity than its homogeneous control catalyst, likely due to the formation of robust single-site catalyst in the MOF through site-isolation.

Chiral Iron(II)-Catalysts within Valinol-Grafted Metal-Organic Frameworks for Enantioselective Reduction of Ketones

The development of highly efficient and enantioselective heterogeneous catalysts based on earth-abundant elements and inexpensive chiral ligands is essential for environment-friendly and economical production of optically active compounds. We report a strategy of synthesizing chiral amino alcohol-functionalized metal-organic frameworks (MOFs) to afford highly enantioselective single-site base-metal catalysts for asymmetric organic transformations. The chiral MOFs (vol-UiO) were prepared by grafting of chiral amino alcohol such as l-valinol within the pores of aldehyde-functionalized UiO-MOFs via formation of imine linkages. The metalation of vol-UiO with FeCl2 in THF gives amino alcohol coordinated octahedral FeII species of vol-FeCl(THF)3 within the MOFs as determined by X-ray absorption spectroscopy. Upon activation with LiCH2SiMe3, vol-UiO-Fe catalyzed hydrosilylation and hydroboration of a range of aliphatic and aromatic carbonyls to afford the corresponding chiral alcohols with enantiomeric excesses up to 99%. Vol-UiO-Fe catalysts have high turnover numbers of up to 15 ?000 and could be reused at least 10 times without any loss of activity and enantioselectivity. The spectroscopic, kinetic, and computational studies suggest iron-hydride as the catalytic species, which undergoes enantioselective 1,2-insertion of carbonyl to give an iron-alkoxide intermediate. The subsequent σ-bond metathesis between Fe-O bond and Si-H bond of silane produces chiral silyl ether. This work highlights the importance of MOFs as the tunable molecular material for designing chiral solid catalysts based on inexpensive natural feedstocks such as chiral amino acids and base-metals for asymmetric organic transformations.

Enantioselective α-Arylation of Primary Alcohols under Sequential One-Pot Catalysis

Secondary benzylic alcohols and diarylmethanols are common structural motifs of biologically active and medicinally relevant compounds. Here we report their enantioselective synthesis by α-arylation of primary aliphatic and benzylic alcohols under sequential catalysis integrating a Ru-catalyzed hydrogen transfer oxidation and a Ru-catalyzed nucleophilic addition. The method can be applied to various alcohols and aryl nucleophiles tolerating a range of functional groups, including secondary alcohols, ketones, alkenes, esters, NH amides, tertiary amines, aryl halides, and heterocycles.

Exploration of highly electron-rich manganese complexes in enantioselective oxidation catalysis; A focus on enantioselective benzylic oxidation

The direct enantioselective hydroxylation of benzylic C-H bonds to form chiral benzylic alcohols represents a challenging transformation. Herein, we report on the exploration of new biologically inspired manganese and iron complexes bearing highly electron-rich aminopyridine ligands containing 4-pyrrolidinopyridine moieties ((S,S)-1, (R,R)-1, 2 and 5) in combination with chiral bis-pyrrolidine and N,N-cyclohexanediamine backbones in enantioselective oxidation catalysis with aqueous H2O2. The current manganese complexes outperform the analogous manganese complexes containing 4-dimethylaminopyridine moieties (3 and 4) in benzylic oxidation reactions in terms of alcohol yield while keeping similar ee values (～60% ee), which is attributed to the higher basicity of the 4-pyrrolidinopyridine group. A detailed investigation of different carboxylic acid additives in enantioselective benzylic oxidation provides new insights into how to rationally enhance enantioselectivities by means of proper tuning of the environment around the catalytic active site, and has resulted in the selection of Boc-l-Tert-leucine as the preferred additive. Using these optimized conditions, manganese complex 2 was shown to be effective in the enantioselective benzylic oxidation of a series of arylalkane substrates with up to 50% alcohol yield and 62% product ee. A final set of experiments also highlights the use of the new 4-pyrrolidinopyridine-based complexes in the asymmetric epoxidation of olefins (up to 98% epoxide yield and >99% ee).

Highly Active Cooperative Lewis Acid—Ammonium Salt Catalyst for the Enantioselective Hydroboration of Ketones

Enantiopure secondary alcohols are fundamental high-value synthetic building blocks. One of the most attractive ways to get access to this compound class is the catalytic hydroboration. We describe a new concept for this reaction type that allowed for exceptional catalytic turnover numbers (up to 15 400), which were increased by around 1.5–3 orders of magnitude compared to the most active catalysts previously reported. In our concept an aprotic ammonium halide moiety cooperates with an oxophilic Lewis acid within the same catalyst molecule. Control experiments reveal that both catalytic centers are essential for the observed activity. Kinetic, spectroscopic and computational studies show that the hydride transfer is rate limiting and proceeds via a concerted mechanism, in which hydride at Boron is continuously displaced by iodide, reminiscent to an SN2 reaction. The catalyst, which is accessible in high yields in few steps, was found to be stable during catalysis, readily recyclable and could be reused 10 times still efficiently working.

Tridentate nitrogen phosphine ligand containing arylamine NH as well as preparation method and application thereof

The invention discloses a tridentate nitrogen phosphine ligand containing arylamine NH as well as a preparation method and application thereof, and belongs to the technical field of organic synthesis. The tridentate nitrogen phosphine ligand disclosed by the invention is the first case of tridentate nitrogen phosphine ligand containing not only a quinoline amine structure but also chiral ferrocene at present, a noble metal complex of the type of ligand shows good selectivity and extremely high catalytic activity in an asymmetric hydrogenation reaction, meanwhile, a cheap metal complex of the ligand can also show good selectivity and catalytic activity in the asymmetric hydrogenation reaction, and is very easy to modify in the aspects of electronic effect and space structure, so that the ligand has huge potential application value. A catalyst formed by the ligand and a transition metal complex can be used for catalyzing various reactions, can be used for synthesizing various drugs, and has important industrial application value.

Iridium-Catalyzed Enantioselective Transfer Hydrogenation of Ketones Controlled by Alcohol Hydrogen-Bonding and sp3-C?H Noncovalent Interactions

Iridium-catalyzed enantioselective transfer hydrogenation of ketones with formic acid was developed using a prolinol-phosphine chiral ligand. Cooperative action of the iridium atom and the ligand through alcohol-alkoxide interconversion is crucial to facilitate the transfer hydrogenation. Various ketones including alkyl aryl ketones, ketoesters, and an aryl heteroaryl ketone were competent substrates. An attractive feature of this catalysis is efficient discrimination between the alkyl and aryl substituents of the ketones, promoting hydrogenation with the identical sense of enantioselection regardless of steric demand of the alkyl substituent and thus resulting in a rare case of highly enantioselective transfer hydrogenation of tert-alkyl aryl ketones. Quantum chemical calculations revealed that the sp3-C?H/π interaction between an sp3-C?H bond of the prolinol-phosphine ligand and the aryl substituent of the ketone is crucial for the enantioselection in combination with O?H???O/sp3-C?H???O two-point hydrogen-bonding between the chiral ligand and carbonyl group. (Figure presented.).