I-Phenylethanol

Dimethyl-2-butanol 4-Methyl-2-pentanol 2-Octanol I-Phenylethanol I-Phenvlethanol 1 -(4-Nitrophenyl)ethaiml 4-Phenyl-3-buten-2-ol ... 

Nitrile I-CyanO 2,2,2-trifluoro-I-phenylethanol. 2,2,2-Trifluoroacetophenone cyanohydrin CqH[Pg.608]

Figure 2.24, Determination of the enantiomeric excess of 1-phenylethanol [30, 0.1 mmol in 0.3 ml CDCI3, 25 °C] by addition of the chiral praseodymium chelate 29b (0.1 mmol), (a, b) H NMR spectra (400 MHz), (a) without and (b) with the shift reagent 29b. (c, d) C NMR spectra (100 MHz), (c) without and (d) with the shift reagent 29b. In the C NMR spectrum (d) only the C-a atoms of enantiomers 30R and 30S are resolved. The H and C signals of the phenyl residues are not shifted these are not shown for reasons of space. The evaluation of the integrals gives 73 % R and 27 % S, i.e. an enantiomeric excess (ee) of 46 %...

FIGURE 4.24 Adsorption chromatography of small molecules with a TSK-GEL G2500PWxl column. Column TSK-GEL G2500PWxl, 6 /tm, 7.8 mm X 30 cm. Sample (I) phenylacetic acid. (2) 3-phenylpropionic acid, (3) 4-phenylbutyric acid, (4) benzylamine, (5) 2-phenylethylamine, (6) 3-phenylpropylamine, (7) benzyl alcohol, (8) 2-phenylethanol, and (9) 3-phenyl-1 -propanol. Elution 0.1 M NaCIO, in water. Flow rate 2.0 ml/min. Temperature 65 C. Detection UV at 215 nm. 

A single isomer of 4-phenylperhydropyrido[2,l-c][l,4]oxazin-l-one 319 was isolated from a reaction mixture of 2-bromocyclohexane and 2-azido-2-phenylethanol. The formation of 319 was deduced from azepino[l,2-i]... 

Chitin (Fig. 27) was supported on silica by grinding the two solids together. The Pt complex was tested as a catalyst in the enantioselective hydrogenation of racemic 1-phenylethanol to obtain (i )-l-cyclohexylethanol [82]. Up to 65% yield with 100% ee was obtained and the catalyst was reused five times with almost the same results. 

We investigated lipase-catalyzed acylation of 1-phenylethanol in the presence of various additives, in particular an E. additive using diisopropyl ether as solvent. Enhanced enantioselectivity was obtained when a BEG-hased novel IE, i.e., imidazolium polyoxyethylene(lO) cetyl sulfate, was added at 3-10 mol% vs. substrate in the Burkholderia cepacia lipase (hpase PS-C) catalyzed transesterification using vinyl acetate in diisopropyl ether or a hexane solvent system. ... 

While Josiphos 41 also possessed an element of atom-centered chirality in the side chain, Reetz reported a new class of ferrocene-derived diphosphines which had planar chirality only ligands 42 and 43, which have C2- and C -symmetry, respectively.87 Rhodium(i)-complexes of ligands (—)-42 and (—)-43 were used in situ as catalysts (0.75 mol%) for the hydroboration of styrene with catecholborane 1 for 12 h in toluene at — 50 °C. The rhodium/ i-symmetric (—)-43 catalyst system was the more enantioselective of the two - ( -l-phenylethanol was afforded with 52% and 77% ee with diphosphines (—)-42 and (—)-43, respectively. In both cases, the regioselectivity was excellent (>99 1). With the same reaction time but using DME as solvent at lower temperature (—60 °C), the rhodium complex of 43 afforded the alcohol product with an optimum 84% ee. 

M. Mons, E Piuzzi, I. Dimicoli, A. Zehnacker, and F. Lahmani, Binding energy of hydrogen bonded complexes of the chiral molecule 1 phenylethanol, as studied by 2C R2PI Comparison between diastereoisomeric complexes with butan 2 ol and the singly hydrated complex. Phys. Chem. Chem. Phys. 2, 5065 5070 (2000). 

Fig. 13 Calculated structures of the neutral homochiral (a) and heterochiral (b) complexes between (i )-l-phenylethanol (E ) and 2-pyrrolidinmethanols (ERand P5).

Racemization of chiral a-methyl benzyl cation/methanol adducts. The rate of exchange between water and the chiral labeled alcohols as a function of racemization has been extensively used as a criterion for discriminating the Sn2 from the SnI solvolytic mechanisms in solution. The expected ratio of exchange vs. racemization rate is 0.5 for the Sn2 mechanism and 1.0 for a pure SnI process. With chiral 0-enriched 1-phenylethanol in aqueous acids, this ratio is found to be equal to 0.84 0.05. This value has been interpreted in terms of the kinetic pattern of Scheme 22 involving the reversible dissociation of the oxonium ion (5 )-40 (XOH = H2 0) to the chiral intimate ion-dipole pair (5 )-41 k-i > In (5 )-41, the leaving H2 0 molecule does not equilibrate immediately with the solvent (i.e., H2 0), but remains closely associated with the ion. This means that A inv is of the same order of magnitude of In contrast, the rate constant ratio of... 

K(,SiW 02 )Mn I I) Manganese ion-substituted silicon polyoxotungstate can be used as a mediator for alcohol oxidation. Constant potential electrolysis of 1-phenylethanol at 1.25 V in the presence of 5 mol% of the catalyst gave acetophenone in 61% yield [33]. 

Chemoselectivity is often a major issue in the reduction of multifunctional organic substrates such as substituted conjugated enones. The corresponding unsaturated alcohols have found use as building blocks for pharmaceutically active molecules for example (i-amino-a-phenylethanol is used for the synthesis of (5-blockers which are the active molecules for controlling hypertension and other cardiac disorders. 

The cationic complex [Ir(CO)(ic -N,N,N-(S,S)- Pr-pybox)][PF,5] [50] was also found to be catalytically active in the addition of Ph2SiPt2 to acetophenone, with complete conversion of the ketone into the corresponding silyl ether (I) at room temperature after 72 h of reaction. However, desilylation of the product (I) led to racemic 1-phenylethanol, which means that the reduction took place without asymmetric induction. 

TeClf catalysed Friedel-Crafts aromatic alkylation (typical procedure. To a solution of 1-phenylethanol (3.7 g, 30 mmol) in toluene (30 mL) is added slowly TeCl4 (9.7 g, 36 mmol), keeping the temperature at 25°C (exothermic reaction). Small amounts of white precipitate appear immediately, and after a few minutes the colour of the mixture becomes dark brown. The mixture is stirred for 3 h and then quenched with HgO (20 mL). The organic layer is separated, washed with brine (2x20 mL) and dried (MgS04). Evaporation of the solvent leaves an oily residue which is distilled under vacuum, giving a mixture of 1-phenyl-1-tolylethanes (4.9 g (83.3%) b.p. 117-128°C/1 torr). GLC analysis (silicone OV-101, 0.24 mm X 30 m capillary column at 100-260°C, 4°C min i) reveals an ortholpara ratio of 12 88. 

The use of a chiral polymer instead of the achiral polymers in XXXIX and XXXX allows an asymmetric synthesis. An example is the stereoselective reduction of acetophenone to (I )-l-phenylethanol in 76-97% enantiomeric excess by using the indicated chiral support (Eq. 9-69) [Itsuno et al., 1985] ... 

The correlation between the coverage of surface platinum atoms by bismuth adatoms (Ggi) and the measured rate of 1-phenylethanol oxidation was studied on unsupported platinum catalysts. An electrochemical method (cyclic voltammetry) was applied to determine G i and a good electric conductivity of the sample was necessary for the measurements. The usual chemisorption measurements have the disadvantage of possible surface restructuring of the bimetallic system at the pretreatment temperature. Another advantage of the electrochemical polarization method is that the same aqueous alkaline solution may be applied for the study of the surface structure of the catalyst and for the liquid phase oxidation of the alcohol substrate. 

Figure 20. Simultaneous enantiomer separation of various classes of compounds ( Schurig test mixture 184) on CP-Cyclodextrin-/3-2,3,6-M-19 (permethylatcd /3-cyclodextrin in OV-1701) [25 m x 0.25 mm (i.d.) column, 70°C for 5 min followed by 3cC/miu, 0.65 bar hydrogen]143. 1+2 2,6,6-trimethylbicy-clo[3.1.1]hept-2-ene (x-pinene), 3 ( + )-(lJR)-//ms-2,6,6-trimethylbicyclo[3.1. l]heptane (pinane), 4 (-)-(lS )-fra/M-pinanc. 5 (-)-(lS)-fw-pinane, 6 ( + )-(l/J)-cw-pinane, 7 + 8 2,3-butancdiol. 9 meso-2,3-butanediol, 10 + 11 tetrahydro-5-methyl-2-furanone (y-valerolactone). 12 + 13 1-phenylethanaminc. 14 + 15 1-phenylethanol, 16 + 17 2-ethylhexanoic acid.

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