通过氧化降冰片二烯合成 5-取代呋喃基氨基甲酸酯及其反应活性
Synthesis and Reactivity of 5-Substituted Furfuryl Carbamates via Oxanorbornadienes.
机构信息
School of Chemistry and Biochemistry, Georgia Institute of Technology , Atlanta, Georgia 30332-0400, United States.
出版信息
Org Lett. 2017 Jun 2;19(11):2833-2836. doi: 10.1021/acs.orglett.7b00990. Epub 2017 May 16.
Abstract
Furfuryl carbamates are labile and require care to be accessed by activating furfuryl alcohols. An alternative oxanorbornadiene (OND)-based strategy is presented for the preparation of 5-R-substituted furfuryl carbamates via the reactions of amines with intermediate OND carbonates. The resulting OND carbamates, which are stable for several months, undergo thiol mediated retro-Diels-Alder reaction to deliver the desired furfuryl carbamates in a single flask. Conditions for the selective hydrolysis of furfuryl carbamates in the presence of tert-butyloxycarbonyl (Boc) groups were identified, and it was shown that furfuryl carbamates can be used as a prodrug handle.
摘要
糠基氨基甲酸酯不稳定，需要小心处理才能使糠基醇活化。本文提出了一种替代的降冰片二烯（OND）基策略，通过胺与中间的 OND 碳酸酯反应来制备 5-R-取代的糠基氨基甲酸酯。得到的 OND 氨基甲酸酯在几个月内稳定，通过硫醇介导的反-Diels-Alder 反应，在一个烧瓶中一步得到所需的糠基氨基甲酸酯。本文还确定了在叔丁氧羰基（Boc）基团存在下选择性水解糠基氨基甲酸酯的条件，并表明糠基氨基甲酸酯可用作前药。
相似文献
1
Synthesis and Reactivity of 5-Substituted Furfuryl Carbamates via Oxanorbornadienes.通过氧化降冰片二烯合成 5-取代呋喃基氨基甲酸酯及其反应活性
Org Lett. 2017 Jun 2;19(11):2833-2836. doi: 10.1021/acs.orglett.7b00990. Epub 2017 May 16.
2
Convenient method for the preparation of carbamates, carbonates, and thiocarbonates.制备氨基甲酸酯、碳酸酯和硫代碳酸酯的简便方法。
Org Lett. 2007 Dec 6;9(25):5231-4. doi: 10.1021/ol7024108. Epub 2007 Nov 15.
3
The Influence of Substitution on Thiol-Induced Oxanorbornadiene Fragmentation.取代基对巯基诱导的降冰片二烯碎片反应的影响。
Org Lett. 2021 May 7;23(9):3751-3754. doi: 10.1021/acs.orglett.1c01164. Epub 2021 Apr 14.
4
Phosphoryloxymethyl carbamates and carbonates--novel water-soluble prodrugs for amines and hindered alcohols.磷酰氧基甲基氨基甲酸酯和碳酸酯——用于胺类和受阻醇类的新型水溶性前药。
Pharm Res. 1993 Sep;10(9):1350-5. doi: 10.1023/a:1018934200343.
5
Modular degradable hydrogels based on thiol-reactive oxanorbornadiene linkers.基于硫醇反应性氧杂降冰片二烯连接体的模块化可降解水凝胶。
J Am Chem Soc. 2015 Apr 22;137(15):4984-7. doi: 10.1021/jacs.5b02708. Epub 2015 Apr 14.
6
Theoretical Analysis of the Retro-Diels-Alder Reactivity of Oxanorbornadiene Thiol and Amine Adducts.氧杂降冰片二烯硫醇和胺加合物的逆 Diels-Alder 反应的理论分析。
Org Lett. 2017 Sep 1;19(17):4504-4507. doi: 10.1021/acs.orglett.7b02064. Epub 2017 Aug 17.
7
Fluorous Boc ((F)Boc) carbamates: new amine protecting groups for use in fluorous synthesis.氟代叔丁氧羰基（(F)Boc）氨基甲酸酯：用于氟代合成的新型胺保护基团。
J Org Chem. 2001 Jun 15;66(12):4261-6. doi: 10.1021/jo010111w.
8
Iron-Catalyzed Reaction of Urea with Alcohols and Amines: A Safe Alternative for the Synthesis of Primary Carbamates.铁催化尿素与醇类和胺类的反应：一种合成伯氨基甲酸酯的安全替代方法。
ChemSusChem. 2016 Aug 23;9(16):2233-8. doi: 10.1002/cssc.201600587. Epub 2016 Jul 12.
9
Parallel synthesis of ureas and carbamates from amines and CO2 under mild conditions.在温和条件下由胺和 CO2 平行合成脲和氨基甲酸酯。
Org Lett. 2010 Mar 19;12(6):1340-3. doi: 10.1021/ol100259j.
10
Facile one-pot synthesis of unsymmetrical ureas, carbamates, and thiocarbamates from Cbz-protected amines.Cbz 保护胺的一锅法合成不对称脲、氨基甲酸酯和硫代氨基甲酸酯。
Org Biomol Chem. 2016 Jul 26;14(30):7345-53. doi: 10.1039/c6ob01290f.
引用本文的文献
1
Accelerated Mechanophore Activation and Drug Release in Network Core-Structured Star Polymers Using High-Intensity Focused Ultrasound.利用高强度聚焦超声实现网络核心结构星形聚合物中机械活性基团的加速活化和药物释放。
Small Sci. 2024 Jun 17;4(8):2400082. doi: 10.1002/smsc.202400082. eCollection 2024 Aug.
2
Experimental and Theoretical Analysis of the Thiol-Promoted Fragmentation of 2-Halo-3-tosyl-oxanorbornadienes.硫醇促进的2-卤代-3-对甲苯磺酰氧基降冰片二烯碎片化反应的实验与理论分析
Org Lett. 2023 Oct 20;25(41):7481-7485. doi: 10.1021/acs.orglett.3c02548. Epub 2023 Oct 10.
3
Experimental and Theoretical Exploration of the Kinetics and Thermodynamics of the Nucleophile-Induced Fragmentation of Ylidenenorbornadiene Carboxylates.亚烷基降冰片二烯羧酸酯亲核试剂诱导碎片化反应的动力学和热力学的实验与理论探索
J Org Chem. 2023 Aug 18;88(16):11683-11693. doi: 10.1021/acs.joc.3c00980. Epub 2023 Aug 3.
4
The Influence of Substitution on Thiol-Induced Oxanorbornadiene Fragmentation.取代基对巯基诱导的降冰片二烯碎片反应的影响。
Org Lett. 2021 May 7;23(9):3751-3754. doi: 10.1021/acs.orglett.1c01164. Epub 2021 Apr 14.
5
Azanorbornadienes as Thiol-Reactive Cleavable Linkers.氮杂降冰片烯作为硫醇反应性可裂解连接子。
Org Lett. 2020 Aug 21;22(16):6248-6251. doi: 10.1021/acs.orglett.0c01912. Epub 2020 Aug 5.
本文引用的文献
1
Bioorthogonal prodrug activation driven by a strain-promoted 1,3-dipolar cycloaddition.由应变促进的1,3-偶极环加成驱动的生物正交前药活化
Chem Sci. 2015 Feb 1;6(2):1212-1218. doi: 10.1039/c4sc02574a. Epub 2014 Nov 14.
2
Efficient Liver Targeting by Polyvalent Display of a Compact Ligand for the Asialoglycoprotein Receptor.通过多价展示用于去唾液酸糖蛋白受体的紧凑配体实现高效的肝脏靶向。
J Am Chem Soc. 2017 Mar 8;139(9):3528-3536. doi: 10.1021/jacs.6b12964. Epub 2017 Feb 23.
3
Albumin-Oxanorbornadiene Conjugates Formed ex Vivo for the Extended Circulation of Hydrophilic Cargo.体外形成的白蛋白-氧杂降冰片二烯缀合物用于亲水性货物的延长循环
ACS Chem Biol. 2016 Aug 19;11(8):2320-7. doi: 10.1021/acschembio.6b00444. Epub 2016 Jun 27.
4
Isocyanate-Free Routes to Polyurethanes and Poly(hydroxy Urethane)s.制备聚氨酯和聚（羟基脲烷）的无异氰酸酯路线。
Chem Rev. 2015 Nov 25;115(22):12407-39. doi: 10.1021/acs.chemrev.5b00355. Epub 2015 Oct 30.
5
Amino Acid Carbamates As Prodrugs Of Resveratrol.作为白藜芦醇前药的氨基酸氨基甲酸盐。
Sci Rep. 2015 Oct 14;5:15216. doi: 10.1038/srep15216.
6
Modular degradable hydrogels based on thiol-reactive oxanorbornadiene linkers.基于硫醇反应性氧杂降冰片二烯连接体的模块化可降解水凝胶。
J Am Chem Soc. 2015 Apr 22;137(15):4984-7. doi: 10.1021/jacs.5b02708. Epub 2015 Apr 14.
7
Organic carbamates in drug design and medicinal chemistry.药物设计与药物化学中的有机氨基甲酸酯
J Med Chem. 2015 Apr 9;58(7):2895-940. doi: 10.1021/jm501371s. Epub 2015 Jan 7.
8
First Selective CYP11B1 Inhibitors for the Treatment of Cortisol-Dependent Diseases.用于治疗皮质醇依赖性疾病的首批选择性CYP11B1抑制剂。
ACS Med Chem Lett. 2010 Oct 22;2(1):2-6. doi: 10.1021/ml100071j. eCollection 2011 Jan 13.
9
Framework for identifying chemicals with structural features associated with the potential to act as developmental or reproductive toxicants.用于识别具有与可能作为发育或生殖毒物相关结构特征的化学品的框架。
Chem Res Toxicol. 2013 Dec 16;26(12):1840-61. doi: 10.1021/tx400226u. Epub 2013 Nov 22.
10
Degradable conjugates from oxanorbornadiene reagents.可降解的降冰片二烯试剂轭合物。
J Am Chem Soc. 2012 Apr 11;134(14):6491-7. doi: 10.1021/ja301491h. Epub 2012 Mar 28.
Zotero 插件