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Chemical Structure| 13865-19-5 Chemical Structure| 13865-19-5

Structure of Methyl 4-oxobutanoate
CAS No.: 13865-19-5

Chemical Structure| 13865-19-5

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Corin Wagen ;

Abstract: Chemical synthesis has transformed the ability of scientists and engineers to interact with themolecular world. Yet despite almost two centuries of considerable effort, small-molecule synthesisremains a challenging task. Hundreds ofnew reactions are discovered every year, but few possessthe requisite selectivity and generality needed to be use ful for routine synthesis, and elucidation ofthe ir mechanism and underlying catalytic principles is rarely conducted. In this work, we describea variety of efforts at the interface of organic, computational, and analytical chemistry which seekto address the linked problems of discovering selective organocatalysts and understanding themechanism by which they operate. In Chapter 1, we report the development of a new analytical method that combines chiralstationary phase supercritical fluid chromatography wih mass spectrometry-based detection toenable enantiodetermination of pooled crude reaction mixtures, greatly increasing analyticalthroughput. This advance allows us to perform multi-substrate screening to discover catalystspossessing good substrate scope, which we demonstrate in the optimization of a Bronsted acidcatalyst for the enantioselective Pictet-Spengler reaction.In Chapter 2, we disclose the results of a mechanistic study aimed at understanding a hydrogenchloride/hydrogen-bond donor co-catalyzed Prins cyclization of alkenyl aldehydes whichexhibited dramatic rate acceleration compared to the background reaction. Our studies reveal that the catalyst reacts with hydrogen chloride to form a new chiral acid in siu with a higher pK, thanhydrogen chloride, which nevertheless reacts faster owing to favorable catalyst-controlledpositioning ofthe chloride anion to electrostatically stabilize the major transition state In Chapter 3, we report a computational study of our group's regio- and stereoselectiveglycosylation of` minimally protected glycosyl acceptors. The computational model describedthe first of` hydrogen-bond-donor-catalyzed glycosylation of glycosyl phosphate donors containsfeatures of the transition state previously hypothesized on the basis of experimental results, andlends support to the proposed “4H” binding mechanism. In Chapter 4, we describe the development of an enantioselective protio-semipinacol reactionof unactivated vinylic cyclopropanols. Motivated by the question of how high enantioselectivitycan be achieved in a low-barrier 1,2-rearrangement, we conduct an experimental andcomputational mechanistic investigation and come to the surprising conclusion that protonation toform a formally achiral carbocation in fact exerts stereocontrol over the subsequent rearrangementstep: the rearrangement is so rapid that the carbocation is locked in a given chiral conformationrendering the rearrangement efectively stereospecific. Finally, in chapter 5 we detail a spectroscopic and computational study of solutions ofhydrogen chloride in diethyl ether, aimed at assigning the solution structure ofhydrogen chlorideIn situ IR spectroscopy, combined with density-functional theory and molecular dynamicsprovides evidence for the existence of oxonium ions formed from complete proton transfer todiethyl ether. This observation explains the often-inhibitory effect of diethyl ether on hydrogenchloride-catalyzed reactions and has intriguing implications for catalyst design.

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Product Details of [ 13865-19-5 ]

CAS No. :13865-19-5
Formula : C5H8O3
M.W : 116.12
SMILES Code : O=C(OC)CCC=O
MDL No. :MFCD00082185
InChI Key :DLZVZNAPRCRXEG-UHFFFAOYSA-N
Pubchem ID :83779

Safety of [ 13865-19-5 ]

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H227-H315-H319
Precautionary Statements:P210-P264-P280-P302+P352-P305+P351+P338-P332+P313-P337+P313-P370+P378-P403+P235-P501

Application In Synthesis of [ 13865-19-5 ]

* 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.

  • Downstream synthetic route of [ 13865-19-5 ]

[ 13865-19-5 ] Synthesis Path-Downstream   1~2

  • 1
  • [ 13865-19-5 ]
  • [ 1397-89-3 ]
  • N,N-di-(methyl 4-butanoate)-AmB [ No CAS ]
YieldReaction ConditionsOperation in experiment
45% With hydrogenchloride; water; sodium cyanoborohydride; In N,N-dimethyl-formamide; at 20℃; for 18h; Example 14. Synthesis of N, N-Di- (methyl-4-butanoate) -AmB (15):; To a solution of methyl-4-oxobutanoate (520 mg, 4.50 mmol) and AmB (1) (820 mg, 0.890 mmol) in DMF (5.00 mL) was added NaBH3CN (280 mg, 4.50 mmol) followed by a drop of cone. HCl. After 18 h at room temperature, Amberlite IRA-743 (800 mg) was added and the mixture was stirred for an hour. After filtration, the solution was concentrated down and added dropwise to diethyl ether (250 mL) . The yellow precipitate was filtered and purified by flash chromatography (40-8-1 CHCl3-MeOH-H2O) providing the desired compound 15 as a yellow solid (450 mg, 45%). Rf 0.30 (40-8- 1 CHCl3-MeOH-H2O), 1H NMR (500 MHz, DMSO-de) delta 6.46-6.06 (m, 13H), 5.95 (dd, J = 15, 9 Hz, IH), 5.82 (s, IH), 5.45 (dd, J = 15, 10 Hz, IH), 5.32 (s, IH), 5.21-5.19 (m, IH), 4.80-4.74 (m, 2H), 4.62 (s, IH), 4.43-4.36 (m, IH), 4.32 (s, IH), 4.25-4.17 (m, 2H), 4.06-3.96 (m, 2H), 3.75 (s, IH), 3.58 (s, 6H), 3.55-3.35 (m, OH), 3.11-3.08 (m, IH), 2.78-2.72 (m, IH), 2.64-2.59 (m, IH), 2.31 (t, J = I Hz, 4H), 2.17 (d, J = 6 Hz, IH), 1.98-1.23 (m, 21H), 1.18 (d, J = beta Hz, 3H), 1.11 (d, J = 6 Hz, 3H), 1.04 (d, J = 6 Hz, 3H), 0.92 (d, J = I Hz, 3H), 13C NMR (125 MHz, <n="73"/>DMSO-d6) delta 173.6, 173.2, 170.5, 136.9, 136.7, 133.8, 133.6, 133.5, 133.1, 132.4, 132.3, 132.1, 132.0, 131.8, 131.6, 131.1, 128.7, 97.4, 97.1, 80.3, 77.1, 76.3, 75.7, 74.4, 73.8, 73.7, 73.5, 69.4, 69.2, 68.9, 67.9, 67.6, 66.2, 65.4, 63.9, 56.9, 51.0, 50.2, 46.2, 44.6, 44.2, 42.3, 42.0, 35.0, 31.0, 29.0, 24.0, 18.4, 18.2, 16.9, 12.0; MALDI-TOF calcd for C55H85NO2I [M+H+]+: 1124.6005. Found: 1124.5600.
  • 2
  • [ 13865-19-5 ]
  • [ 1168139-43-2 ]
  • C13H16FNO2 [ No CAS ]
YieldReaction ConditionsOperation in experiment
In dichloromethane; at 20℃; for 0.5h;Inert atmosphere; To a solution of (R)- 1 -(2-fluorophenyl)ethanamine(278 mg, 2.0 mmol, Kingston) in DCM (3.0 mE) was addedmethyl 4-oxobutanoate (232 mg, 2.0 mmol, Aldrich). Thereaction mixture was stirred at room temperature for 30 mm, and Na(OAc)3BH (636 mg, 3.00 mmol) and i-PrOH (2.0 mE) were then added. The reaction mixture was stirred at room temperature for 1 h. The reaction was quenched with MeOH (2.0 mE) and sat. aq. K2HPO4 (2.0 mE) and then diluted with DCM (50 mE). The organic layer was separated, dried over MgSO4, filtered and concentrated in vacuo. The residue was purified by preparative HPEC to provide the desired product (239 mg, 50%) as a white solid. ?H NMR (CDC13) oe 7.37 (td, J=7.5, 1.8 Hz, 1H), 7.21-7.14 (m, 1H), 7.12-7.07 (m, 1H), 6.98 (ddd, J=10.6, 8.1, 1.1 Hz, 1H), 4.09 (q, J=6.6 Hz, 1H),3.62 (s, 3H), 2.58-2.50 (m, 1H), 2.48-2.40 (m, 1H), 2.33 (td, J=7.4, 3.3 Hz, 2H), 1.81-1.73 (m, 2H), 1.35 (d, J=6.6 Hz, 3H); MS(ESI) m/z 240.2 (M+H).
 

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