环张力促进的叠氮-炔环加成反应
摘要
近年來，點擊化學中的環張力促進的疊氮-炔環加成（SPAAC）反應由于具有高效快速、高選擇性和生物正交性等優點被廣泛用于生物醫學和材料科學等多個領域。SPAAC反應不需要光、熱、超聲和催化劑等額外的刺激，反應的驅動力來源于高張力的活潑環狀炔烴，因此合理設計環狀炔烴是SPAAC反應的關鍵。本文詳細歸納了不同環數目的環狀炔烴的穩定性和反應活性，總結參與SPAAC的穩定環狀炔烴，并討論了它們參與SPAAC反應的二級反應速率常數。本文還介紹了目前應用廣泛的代表性環狀炔烴的制備方法研究進展。最后，對無銅催化的SPAAC的應用前景和存在的問題進行討論和展望。 In recent years, strain-promoted azide-alkyne cycloaddition (SPAAC) reaction has been widely used in many fields such as biomedicine and materials science due to its high efficiency, rapidity, high selectivity, and bioorthogonality. SPAAC reaction does not require additional stimuli such as light, heat, ultrasound or catalysts. The driving force of the reaction comes from the active cyclic alkynes with high strain. Therefore, the rational design of the cycloalkynes is the key to the SPAAC reaction. In this review, the stability and reactivity of cycloalkynes with different ring numbers are discussed, and the stable cycloalkynes participating in SPAAC smoothly as well as their second-order reaction rate constants in the SPAAC reaction are summarized. The research progress in the preparation methods of representative cyclic alkynes that are currently widely used is also introduced. Moreover, the application, challenge and future outlook of SPAAC without copper catalysis are discussed and prospected.