CC BY-ND-NC 4.0 · SynOpen 2018; 02(04): 0293-0297
DOI: 10.1055/s-0037-1610401
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Enantioselective Bromolactonization of Deactivated Olefinic Acids­: Studies Toward the Synthesis of Brominated Isochroman-1,4-diones

Danqing Li
a  First Affiliated Hospital of Guangzhou University of Traditional Chinese Medicine, Guangzhou 510405, P. R. of China
,
Hailong He
b  Guangzhou Wanglaoji Pharmaceutical Company Limited, Guangzhou 510450, P. R. of China
,
Xiaodan Huang
b  Guangzhou Wanglaoji Pharmaceutical Company Limited, Guangzhou 510450, P. R. of China
,
Pei Yu*
c  Institute of New Drug Research and Guangzhou Key Laboratory of Innovative Chemical Drug Research in Cardiocerebrovascular Diseases, Jinan University College of Pharmacy, Guangzhou 510632, P. R. of China   Email: pennypeiyu@163.com   Email: chemjxj2015@jnu.edu.cn
,
c  Institute of New Drug Research and Guangzhou Key Laboratory of Innovative Chemical Drug Research in Cardiocerebrovascular Diseases, Jinan University College of Pharmacy, Guangzhou 510632, P. R. of China   Email: pennypeiyu@163.com   Email: chemjxj2015@jnu.edu.cn
› Author Affiliations
We thank the Natural Science Foundation of Guangdong Province (Grant No. 2017B050506006) and Fundamental Research Funds for the Central University (Grant No. 21617470) for financial support.
Further Information

Publication History

Received: 10 October 2018

Accepted after revision: 02 November 2018

Publication Date:
22 November 2018 (online)


These authors contributed equally to this work.

Abstract

Enantioselective bromolactonization using an amino-carbamate­ catalyst to generate brominated isochroman-1,4-diones is described. Excellent yields and moderate enantioselectivities were achieved.

Supporting Information

 
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  • 8 Representative Procedure for Generating α,β-Unsaturated Ketone 4a : To a solution of keto acid A (3.0 mmol, 1.0 equiv) in acetic acid (6 mL) was added pyrrolidine (0.1 mL, 1.2 mmol, 0.4 equiv) and formaldehyde solution (36.5–38% in H2O, 1 mL, 13.2 mmol, 4.4 equiv) at room temperature. The mixture was then stirred for 48 h at 85 °C. After evaporation of the acetic acid, water and EtOAc were added. The organic layer was washed with water, dried over magnesium sulphate and filtered. Concentration of the organic layer afforded the crude product, which was further purified by flash column chromatography (hexane/EtOAc) to give the corresponding α,β-unsaturated ketone 4a. Yield: 427.5 mg (75%); yellow solid; mp 125–126 °C; 1H NMR (CDCl3, 300 MHz): δ = 10.84 (br/ s, 1 H), 8.09–7.33 (m, 4 H), 5.80 (s, 1 H), 5.30 (s, 1 H), 2.07 (s, 3 H); 13C NMR (CDCl3, 75 MHz): δ = 199.2, 170.9, 145.9, 142.7, 133.2, 130.8, 129.4, 127.8, 127.7, 127.6, 17.4; HRMS (TOF): m/z [M – 1] calcd for C11H9O3: 189.0562; found: 189.0561
  • 9 Representative Procedure for Generating Isochroman-1,4-dione 5a : To a solution of α,β-unsaturated ketone 4a (38 mg, 0.2 mmol, 1.0 equiv) and catalyst 15s (14.6 mg, 0.03 mmol, 0.15 equiv)in toluene (8 mL), at 15 °C, in the dark under nitrogen was added NBS (46 mg, 0.26 mmol, 1.3 equiv). The resulting mixture was stirred at 15 °C and monitored by TLC. The reaction was quenched with saturated Na2SO3 (1 mL) at 15 °C and then was allowed to warm to room temperature. The mixture was diluted with water (3 mL), extracted with EtOAc, dried over MgSO4, filtered and concentrated in vacuo. The residue was purified by flash column chromatography (hexane/EtOAc) to yield the corresponding isochroman-1,4-dione 5a. Yield: 53.1 mg (99%); yellow oil; [α]D 25 = 4.9 (c 1.0, MeOH, 73:27 er); 1H NMR (CDCl3, 300 MHz): δ = 8.32–7.83 (m, 4 H), 3.99 (dd, J 1 = 9.0 Hz, J 2 = 93.0 Hz, 2 H), 1.78 (s, 3 H); 13C NMR (CDCl3, 75 MHz): δ = 192.3, 160.9, 135.9, 134.7, 130.7, 130.6, 126.6, 126.4, 87.6, 37.4, 25.4; HRMS (TOF+): m/z [M + H]+ calcd. for C11H10BrO3: 269.1377; found: 269.1378; HPLC (Daicel Chiralcel AD-H; i-PrOH/hexane = 10:90, 1.0 mL/min, 254 nm): t 1 = 8.6 min (major), t 2 = 9.5 min (minor)