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标题: 膦氧甲氧基脫氧蘇糖基腺嘌呤前藥的可擴展合成,體外cccDNA [打印本页]

作者: StephenW    时间: 2020-11-19 14:58     标题: 膦氧甲氧基脫氧蘇糖基腺嘌呤前藥的可擴展合成,體外cccDNA

Scalable Synthesis, In Vitro cccDNA Reduction, and In Vivo Antihepatitis B Virus Activity of a Phosphonomethoxydeoxythreosyl Adenine Prodrug
Min Luo  1 , Shuo Wu  2 , Raj Kalkeri  3 , Roger G Ptak  3 , Tianlun Zhou  4 , Lieve Van Mellaert  5 , Chuanmin Wang  6 , Shrinivas G Dumbre  1 , Timothy Block  4 , Elisabetta Groaz  1 , Steven De Jonghe  7 , Yuhuan Li  2 , Piet Herdewijn  1
Affiliations
Affiliations

    1
    Medicinal Chemistry, KU Leuven, Rega Institute for Medical Research, Herestraat 49-box 1041, 3000 Leuven, Belgium.
    2
    CAMS Key Laboratory of Antiviral Drug Research, Institute of Medicinal Biotechnology, Chinese Academy of Medical Sciences & Peking Union Medical College, No. 1, Tiantan Xili, 100050 Beijing, China.
    3
    Department of Infectious Disease Research, Southern Research Institute, 431 Aviation Way, Frederick, Maryland 21701, United States.
    4
    Baruch S. Blumberg Institute, Doylestown, Pennsylvania 18902, United States.
    5
    Department of Microbiology, Immunology and Transplantation, Laboratory of Molecular Bacteriology, KU Leuven, Rega Institute for Medical Research, Herestraat 49-box 1037, 3000 Leuven, Belgium.
    6
    Department of Infectious Diseases, Taihe Hospital, Hubei University of Medicine, Shiyan, Hubei 442000, China.
    7
    Department of Microbiology, Immunology and Transplantation, Laboratory of Virology and Chemotherapy, KU Leuven, Rega Institute for Medical Research, Herestraat 49-box 1043, 3000 Leuven, Belgium.

    PMID: 33191744 DOI: 10.1021/acs.jmedchem.0c01381

Abstract

Standard literature procedures for the chemical synthesis of l-threose nucleosides generally employ l-ascorbic acid as starting material. Herein, we have explored two alternative routes that start from either l-arabitol or l-diethyl tartrate, both affording 2-O-methyl-l-threofuranose as a key building block for nucleobase incorporation. The access to multigram quantities of this glycosyl donor in a reproducible fashion allows for the preparation of 2'-deoxy-α-l-threofuranosyl phosphonate nucleosides on a large scale. This methodology was applied to the gram scale synthesis of an aryloxy amidate prodrug of phosphonomethoxydeoxythreosyl adenine. This prodrug exerted potent activity against an entecavir-resistant hepatitis B virus (HBV) strain, while leading to a significant reduction in the levels of HBV covalently closed circular DNA in a cellular assay. Furthermore, its remarkable anti-HBV efficacy was also confirmed in vivo using a hydrodynamic injection-based HBV mouse model, without relevant toxicity and systemic exposure occurring.

作者: StephenW    时间: 2020-11-19 14:59

膦氧甲氧基脫氧蘇糖基腺嘌呤前藥的可擴展合成,體外cccDNA還原和體內抗乙型肝炎病毒活性
羅敏1,吳碩2,拉吉·卡爾克里3,羅傑·普塔克3,天倫·週4,利夫·範·梅拉特5,王傳民6,什里尼瓦斯·鄧布利1,提摩西座4,伊麗莎白·格羅茲1,史蒂芬·德·瓊赫7,玉環李2,Piet Herdewijn 1
隸屬關係
隸屬關係

    1個
    藥物化學,魯汶大學,魯加醫學研究所,比利時,魯汶3000,Herestraat 49-box 1041。
    2
    中國醫學科學院北京協和醫學院藥物生物技術研究所抗病毒藥物CAMS重點實驗室,北京天壇西里1000號
    3
    美國馬里蘭州弗雷德里克市431 Aviation Way南部研究所傳染病研究系,美國21701。
    4
    美國賓夕法尼亞州多爾斯敦的Baruch S.Blumberg研究所,美國18902。
    5
    裡加醫學研究所KU Leuven微生物細菌學,免疫學和移植科,分子細菌學實驗室,比利時魯汶3000赫里斯特拉特49-box 1037。
    6
    湖北醫科大學附屬太和醫院傳染病科,湖北十堰442000
    7
    裡加醫學研究所KU Leuven微生物學,免疫學和移植科,病毒學和化學療法實驗室,比利時魯汶3000 Herestraat 49-box 1043。

    PMID:33191744 DOI:10.1021 / acs.jmedchem.0c01381

抽象

用於化學合成l-蘇糖核苷的標准文獻程序通常使用l-抗壞血酸作為起始原料。在這裡,我們已經探索了兩種替代途徑,它們從1-阿拉伯糖醇或酒石酸1-二乙酯開始,都提供了2-O-甲基-1-蘇呋喃糖作為核鹼基摻入的關鍵構件。以可再現的方式獲得數克數量的該糖基供體,使得可以大規模製備2'-脫氧-α-1-蘇呋喃糖基膦酸酯核苷。該方法學用於膦酰基甲氧基脫氧蘇糖基腺嘌呤的芳氧基酰胺化物前藥的克級合成。該前藥對耐恩替卡韋的乙型肝炎病毒(HBV)菌株發揮了有效的作用,同時導致細胞分析中HBV共價閉合環狀DNA的水平顯著降低。此外,還使用基於水動力注射的HBV小鼠模型在體內證實了其卓越的抗HBV功效,而未發生相關毒性和全身性暴露。




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