Structure of 28645-07-0
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The BI-3802 was designed by Boehringer Ingelheim and could be obtained free of charge through the Boehringer Ingelheim open innovation portal opnMe.com, associated with its negative control.
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CAS No. : | 28645-07-0 |
Formula : | C10H12O2 |
M.W : | 164.20 |
SMILES Code : | C[C@@H](C1=CC=CC=C1)C(OC)=O |
MDL No. : | MFCD27578380 |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With C44H60O2P2; copper(II) acetate monohydrate; In toluene; tert-butyl alcohol; for 2h;Inert atmosphere; | Add Cu (OAc) 2 · H2O (2.0mg) to a dry reaction flask replaced with nitrogen(R) -L4 (Ar '= 4-Me-3,5- (t-Bu) 2-Ph) (5.6 mg), toluene (2.0 mL), and stirred at room temperature until a blue solution.Reduce the temperature to -25 , add Poly(methylhydrosiloxane) (120muL) and tert-butanol (182muL) to the above liquid,After stirring for 5 min, methyl 2-phenylacrylate (161 mg) was added.After stirring for 2h, then add saturated NH4Cl solution (4.0mL), continue stirring for 30min, and then separate the liquid,The aqueous phase was extracted with ethyl acetate (3 × 5.0 mL), and the combined organic phase was washed with saturated NaCl solution,The product was dried, concentrated and separated by anhydrous sodium sulfate (149mg, yield 91%, ee 35%,The dominant configuration is (S) -configuration. |
With hydrogen;(S,S)-(-)-2,2'-bis[(R)-(N,N-dimethylamino)(phenyl)methyl]-1,1'-bis[diphenylphosphine]ferrocene; | 0.01 mmol Ru (COD)2X and 0.01 mmol of the ferrocenyl ligand are dissolved in 12 ml of the appropriate solvent in a 25 ml shaker vessel. After the addition of 1 mmol of the unsaturated ester the solution is transferred under argon into a 100 ml steel autoclave and heated after multiple rinsing with H2 for 10 min. at the appropriate hydrogen pressure to reaction temperature. The mixture is then agitated, filtered, (the optionally added acid esterified with Me3SiCHN2) and the enantiomeric excess determined by HPLC [(Chiracel OJ, n-heptane/isopropanol 95:5; flow 0.6 mL/min, T=20 C.; tR=18.05 (S), 21.13 (R)]. alpha-phenylacrylic acid: Solvent: THF Reaction temperature: 60 C. Pressure: 5000 kPa |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With toluene-4-sulfonic acid; lithium chloride;[((S)-(+)-4,12-bis[di(3,5-xylyl)phosphino]-[2.2]-paracyclophane)dipalladium] tetrachloride; In water; butanone; at 25℃; under 22502.3 Torr;Inert atmosphere; | Lithium chloride (8.4 mg, 0.20 mmol), para-toluenesulfonic acid (34.4 mg, 0.20 mmol) and [(Xyl-(S)-Phanephos)Pd2Cl4] (0.01 mmol) were weighed into a 5 ml microwave vial. A stirring bar was added and the vial was sealed with a crimp cap and put under inert atmosphere. Styrene (1 mmol), dry and degassed methanol (1.5 ml) and an internal standard (approximately 10 mul of either tetraethylsilane and 1-methylnaphtalene) were added using a syringe. The solution was mixed before 20 mul of the solution was diluted in CDCl3 and analysed using NMR (to give a t0 spectra that calibrates the internal standard against starting material). The caps were pierced with two needles and quickly placed in an autoclave that had previously been placed under an argon atmosphere before being opened under a flow of argon. The autoclave was sealed, purged three times with CO and then pressurised to 30 bar and heated in a preheated oil bath at 25 C. with constant magnetic stirring. After the desired time, the autoclave was cooled to room temperature and the pressure released slowly. The mixture was then analysed by taking a sample, diluting with CDCl3 and obtaining a 1H NMR spectrum. The solvent was carefully removed from the reaction mixture and the crude product was filtered through a small column packed with Si02 eluting with hexane: ethylacetate 8:1. The solvent was removed to give carboxylic acid ester product as a 47:53 mixture of branched and linear isomers (71% conversion to ester, 62% isolated yield). The ratio of optical isomers was 94.5:5.5.The enantiomeric excess was determined by HPLC, using a Chirapak AD-H, 250×4.6 mm, 5 mum with guard cartridge, n-hexane 100%, 0.5 mL min-1, 210 nm, tR[(+)-S]=17.9 min, tR[(-)-R]=20.0 min, tR[linear]=25.1 min. GCMS shows the expected linear and branched esters. EIMS 164 (M+).NMR data for catalysis products: Methyl-2-phenylpropanoate:1H NMR (300 MHz, CDCl3) delta 1.42 (d, J=9, CH3, 3H), 3.57 (s, CH3, 3H), 3.65 (q, J=9 Hz, CH, 1H), 7.07-7.28 (m, ArH, 5H). 13C NMR (75 MHz, CDCl3) delta 18.6, 45.5, 52.1, 127.2, 127.5, 128.7, 140.5, 175.1.Methyl-3-phenylpropanoate:1H NMR (300 MHz, CDCl3) delta 2.55 (t, J=7.5, CH2, 2H), 2.87 (t, J=7.5, CH2, 2H), 3.58 (s, OCH3, 3H), 7.07-7.28 (m, ArH, 5H). 13C NMR (75 MHz, CDCl3) delta 31.0, 35.7, 51.7, 126.3, 128.3, 128.5, 173.4. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogen;chloro(1,5-cyclooctadiene)rhodium(I) dimer; C40H58FeN2O3P2; In toluene; at 25℃; under 60006.0 Torr; for 23h;Product distribution / selectivity; | The catalyst precursor and the ligand were stirred in the solvent under argon. A solution of the substrate was added, the argon is drawn off with vacuum and the vessel is connected to a hydrogen supply at the given pressure and temperature. Switching on the stirrer starts the hydrogenation. After the given time, the stirrer is switched off and the solution is placed under argon again. Conversion and enantiomeric excess (ee) are determined by gas chromatography. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
General procedure: A 10mL tube equipped with a magnetic stirring bar, substrate (0.5mmol), catalyst (0.005mmol) and KOH (0.05mmol), was vacuum-pumped and flushed with argon three times. A degassed solvent (2mL) was then added and the tube was transferred to a stainless autoclave in a glove box. The autoclave was pressurized and evacuated with hydrogen three times, and finally charged with hydrogen at a pressure of 50atm. The reaction mixture was magnetically stirred at the given temperature for 24h. After cooling to room temperature, the pressure was released. The solvent was removed in vacuo and the crude product was examined by 1H NMR to determine the conversion. The pure product was obtained by flash column chromatography using ethyl acetate/petroleum ether as the eluant. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With amphiphilic resin supported Pro-D-Pro-Aib-Tyr-His-(Leu-Leu-Aib)2; In tetrahydrofuran; at 40℃; for 24h; | To a solution of formylphenyl ester 6 (0.013 mmol) in THF (87 muL), a resin-supportedpeptide catalyst 1 (12 mg, 0.0026 mmol of the terminal prolyl residue) and methanol(174 muL) were added. After stirring the mixture at 40 C for 24 h, the peptide catalystwas filtered off and washed with chloroform. The solvent was removed under reducedpressure, and the residue was analyzed by 1H NMR spectroscopy. Conversion wasdetermined by comparing the ratio of the formyl groups of 6 and salicylaldehyde. Then,the residue was purified by preparative TLC (hexanes/ethyl acetate 4:1) to giverecovered 6 and methyl ester 7. Enantiomeric excess was determined by HPLC analysisusing Chiralcel OJ-H (25 cm) column and OJ-H guard (1 cm). For 6 (eluent:hexanes/2-propanol = 90 : 10, 1.0 mL min-1), tR = 31.0 min (major), 37.8 min (minor). For7 (eluent: hexanes/2-propanol = 99.5 : 0.5, 1.0 mL min-1), tR = 19.7 min (major), 27.9 min(minor). To determine the absolute configuration of the major isomer, recovered 6 was converted to methyl ester 7 by treating 6 with DBU in methanol. According to aliterature,2 the major configuration of 7 was assigned. |