Asymmetric Chlorination of 4-Substituted Pyrazolones Catalyzed by Chiral Copper Complexes

Xue-Yang Chen; Zhen-Hui Jiang; Wan-Zhen Ju; Hao Yin; Suo-Suo Qi; Ming-Ming Chu; Yi-Feng Wang

doi:10.1055/s-0039-1690879

Synlett, Table of Contents

Synlett 2020; 31(13): 1318-1322
DOI: 10.1055/s-0039-1690879

letter

Asymmetric Chlorination of 4-Substituted Pyrazolones Catalyzed by Chiral Copper Complexes

Authors

Xue-Yang Chen

State Key Laboratory Breeding Base of Green Chemistry-Synthesis Technology, Key Laboratory of Green Pesticides and Cleaner Production Technology of Zhejiang Province, Zhejiang University of Technology, Hangzhou 310014, P. R. of China Email: wangyifeng@zjut.edu.cn
Zhen-Hui Jiang
Wan-Zhen Ju
Hao Yin
Suo-Suo Qi
Ming-Ming Chu
Yi-Feng Wang∗

Abstract

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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.

Key words

asymmetric catalysis - copper catalysis - bisoxazolines - chlorination - pyrazolones

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References

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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.

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