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Chemical Structure| 585-74-0

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Product Citations

Siriboe, Mary G ; Vargas, David A ; Fasan, Rudi ;

Abstract: Chiral cyclopropanols are highly desirable building blocks for medicinal chemistry, but the stereoselective synthesis of these molecules remains challenging. Here, a novel strategy is reported for the diastereo- and enantioselective synthesis of cyclopropanol derivatives via the biocatalytic asymmetric cyclopropanation of vinyl esters with ethyl diazoacetate (EDA). A dehaloperoxidase enzyme from Amphitrite ornata was repurposed to catalyze this challenging cyclopropanation reaction, and its activity and stereoselectivity were optimized via protein engineering. Using this system, a broad range of electron-deficient vinyl esters were efficiently converted to the desired cyclopropanation products with up to 99.5:0.5 diastereomeric and enantiomeric ratios. In addition, the engineered dehaloperoxidase-based biocatalyst is able to catalyze a variety of other abiological carbene transfer reactions, including N−H/S−H carbene insertion with EDA as well as cyclopropanation with diazoacetonitrile, thus adding to the multifunctionality of this enzyme and defining it as a valuable new scaffold for the development of novel carbene transferases.

Alternative Products

Product Details of 3′-Methylacetophenone

CAS No. :585-74-0
Formula : C9H10O
M.W : 134.18
SMILES Code : CC(C1=CC=CC(C)=C1)=O
MDL No. :MFCD00008742
InChI Key :FSPSELPMWGWDRY-UHFFFAOYSA-N
Pubchem ID :11455

Safety of 3′-Methylacetophenone

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H315-H319-H335
Precautionary Statements:P261-P305+P351+P338

Application In Synthesis of 3′-Methylacetophenone

* 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.

  • Upstream synthesis route of [ 585-74-0 ]
  • Downstream synthetic route of [ 585-74-0 ]

[ 585-74-0 ] Synthesis Path-Upstream   1~2

  • 1
  • [ 400-38-4 ]
  • [ 585-74-0 ]
  • [ 53764-99-1 ]
YieldReaction ConditionsOperation in experiment
87% With sodium methylate In toluene for 4 h; Reflux To a solution of isopropyl 2,2,2-trifluoroacetate 10 (7.40g, 0.0474mol) in toluene (15 mL) was added and 3’-methylacetophenone 11 (6.36g, 0.0474mol) and cooled to 0°C, followed by dropwise addition Sodium methoxide (3.0g, 0.0616 mol) to the reaction mixture. The reaction mixture was heated to reflux. After stirring for 4 h, the reaction mixture was diluted with water (275 mL), brine (275 mL), EtOAc (500 mL). The aqueous layer was separated and extracted with EtOAc (200 mL x 4). The combined organic phases were washed with brine (500 mL x 1), dried over Na2SO4 and concentrated under vacuum. The crude product purified by flash column chromatography to give 4,4,4-trifluoro-1-(m-tolyl)butane-1,3-dione, 8 as a white solid (9.5g, 87percent yield). To a 500 mL round-bottomed flask containing ethyl acetate (20 mL) and water (16 mL) was added 4,4,4-trifluoro-1-(m-tolyl)butane-1,3-dione 8 (4.0g, 0.0174mol), the reaction mixture was cooled to 0°C and stirred for 15 min. 4-hydrazinobenzenesulfonamide hydrochloride7 (4.0g, 0.0214 mol) was added to the reaction mixture slowly. The reaction was refluxed for 8 h then cooled to rt. The solid precipitated on cooling was filtered, the filtered solid was washed with cold isopropyl alcohol (20mL X 2) to give the the impurity A 2 as white solid (5.15g) with an excellent yield of 92.0percent. 4-(5-(m-tolyl)-3-(trifluoromethyl)-1H-pyrazol-1-yl)benzenesulfonamide (2) 1H NMR (400 MHz, DMSO - d6) δ 7.94 – 7.79 (m, 2H), 7.60 – 7.45 (m, 4H), 7.21 (dd, J = 10.9, 5.1 Hz, 4H), 7.08 – 6.89 (m, 1H), 2.25 (s, 3H). 13C NMR(101 MHz, DMSO - d6) δ 145.82, 144.54, 142.86, 142.45, 141.59, 138.80, 130.57, 130.04, 129.18, 128.69, 127.31, 126.51, 121.86 (q, J = 265 Hz), 106.91, 21.42. 19F NMR (376 MHz, DMSO - d6) δ -60.77. HRMS m/z (M-H)-: 380.0695; calculated for C17H14F3N3O2S; 380.0686
References: [1] Bulletin of the Korean Chemical Society, 2019, .
  • 2
  • [ 383-63-1 ]
  • [ 585-74-0 ]
  • [ 53764-99-1 ]
References: [1] Organic and Biomolecular Chemistry, 2016, vol. 14, # 5, p. 1531 - 1535.
[2] Journal of Medicinal Chemistry, 1997, vol. 40, # 9, p. 1347 - 1365.
[3] Bioorganic and Medicinal Chemistry Letters, 2004, vol. 14, # 2, p. 499 - 504.
[4] Bioorganic and Medicinal Chemistry, 2018, vol. 26, # 12, p. 3406 - 3413.
 

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