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Synlett 2020; 31(13): 1318-1322
DOI: 10.1055/s-0039-1690879
DOI: 10.1055/s-0039-1690879
letter
Asymmetric Chlorination of 4-Substituted Pyrazolones Catalyzed by Chiral Copper Complexes
Authors
The research was supported by the National Key R & D Program of China (2017YFB0307200).
Weitere Informationen
Publikationsverlauf
Received: 27. Februar 2020
Accepted after revision: 13. März 2020
Publikationsdatum:
31. März 2020 (online)
Abstract
A fast and highly enantioselective chlorination of 4-pyrazolones catalyzed by bis(oxazoline)–Cu(ClO4)2·6H2O complexes has been developed. Under the optimized conditions, a series of pyrazolones bearing stereogenic chlorine-attached carbon centers were obtained in moderate to high yields (up to 98%) and with enantioselectivities of up to 98% ee.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0039-1690879.
- Supporting Information (PDF)
-
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- 10 Chloropyrazolones 3a–t; General Procedure A test tube was charged with Cu(ClO4)2 ·6H2O (3.7 mg, 0.01 mmol), bisoxazoline Ia (4.6 mg, 0.01 mmol), and CH2Cl2 (1.0 mL), and the solution was stirred at r.t. for 0.5 h then cooled to –40 °C for 20 min. The appropriate pyrazolone 1 (0.1 mmol) and DCDMH (1.1 equiv, 0.11 mmol) were added and the mixture was stirred for 0.5 h until the reaction was complete (TLC). The mixture was then warmed to r.t. and purified directly by column chromatography (silica gel). The enantiomeric excess was determined by HPLC on a Chiralpak OD-H, AD-H, or OJ-H column. (4R)-4-Benzyl-4-chloro-2,5-diphenyl-2,4-dihydro-3H-pyrazol-3-one (3a) Yellow oil; yield: 35.3 mg (98%, 98% ee). [α]D 20 +64 (c 1.00, CH2Cl2). HPLC [Daicel Chiralpak AD-H, hexane–i-PrOH (90:10), 1.0 mL/min; λ = 336 nm]: t R (major) = 10.026 min, t R (minor) = 7.373 min. 1H NMR (500 MHz, CDCl3): δ = 8.14–8.05 (m, 2 H), 7.77–7.71 (m, 2 H), 7.60–7.50 (m, 3 H), 7.43–7.35 (m, 2 H), 7.26–7.19 (m, 1 H), 7.17–7.10 (m, 1 H), 7.11–7.04 (m, 2 H), 6.91–6.84 (m, 2 H), 3.78 (d, J = 13.2 Hz, 1 H), 3.71 (d, J = 13.2 Hz, 1 H). 13C NMR (126 MHz, CDCl3) δ = 169.56, 155.09, 137.10, 131.91, 131.04, 129.76, 129.64, 128.99, 128.86, 128.43, 128.01, 126.82, 125.96, 119.54, 64.42, 44.04. HRMS (ESI+): m/z [M + H]+ calcd for C22H18ClN2O: 361.1102; found: 361.1098.
For reviews, see:
For selected examples, see:
For selected examples of enantioenriched pyrazolone derivatives, see:
For reviews, see:
For selected examples, see: