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首页> 外文期刊>Chemistry: A European journal >Strain-Promoted Azide-Alkyne Cycloaddition with Ruthenium(II)-Azido Complexes
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Strain-Promoted Azide-Alkyne Cycloaddition with Ruthenium(II)-Azido Complexes

机译：应变促进的叠氮化物-炔烃环加成反应与钌（II）-叠氮基配合物

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摘要

The reactivity of an exemplary ruthenium(II)-azido complex towards non-activated, electron-deficient, and towards strain-activated alkynes at room temperature and low millimolar azide and alkyne concentrations has been investigated. Non-activated terminal and internal alkynes failed to react under such conditions, even under copper(I) catalysis conditions. In contrast, as expected, rapid cycloaddition was observed with electron-deficient dimethyl acetylenedicarboxylate (DMAD) as the dipolarophile. Since DMAD and related propargylic esters are excellent Michael acceptors and thus unsuitable for biological applications, we investigated the reactivity of the azido complex towards cycloaddition with derivatives of cyclooctyne (OCT), bicyclo-[6.1.0]non-4-yne (BCN), and azadibenzocyclooctyne (ADIBO). While no reaction could be observed in the case of the less strained cyclooctyne OCT, the highly strained cyclooctynes BCN and ADIBO readily reacted with the azido complex, providing the corresponding stable triazolato complexes, which were amenable to purification by conventional silica gel column chromatography. An X-ray crystal structure of an ADIBO cycloadduct was obtained and verified that the formed 1,2,3-triazolato ligand coordinates the metal center through the central N2 atom. Importantly, the determined second-order rate constant for the ADIBO cycloaddition with the azido complex (k_2=6.9 × 10~(-2)m~(-1) s~(-1)) is comparable to the rate determined for the ADIBO cycloaddition with organic benzyl azide (k_2=4.0 × 10~(-1)m~(-1) s~(-1)). Our results demonstrate that it is possible to transfer the concept of strain-promoted azide-alkyne cycloaddition (SPAAC) from purely organic azides to metal-coordinated azido ligands. The favorable reaction kinetics for the ADIBO-azido-ligand cycloaddition and the well-proven bioorthogonality of strain-activated alkynes should pave the way for applications in living biological systems.
机译：已经研究了示例性钌（II）-叠氮基络合物在室温和低毫摩尔叠氮化物​​和炔烃浓度下对未活化的，电子不足的以及对应变活化的炔烃的反应性。在这种条件下，即使在铜（I）催化条件下，未活化的末端炔烃和内部炔烃也无法反应。相反，如所预期的，观察到快速电子加成环与缺电子的乙炔二羧酸二甲酯（DMAD）作为双极性亲和剂。由于DMAD和相关的炔丙基酯是出色的Michael受体，因此不适合生物学应用，因此我们研究了叠氮基络合物与环辛炔（OCT），双环[[6.1.0] non-4-yne（BCN）衍生物的环加成反应性，以及azadibenzocyclooctyne（ADIBO）。虽然在应变较小的环辛炔OCT的情况下未观察到反应，但应变较大的环辛炔BCN和ADIBO容易与叠氮基络合物反应，提供了相应的稳定的三唑并合物，可以通过常规硅胶柱色谱纯化。获得了ADIBO环加合物的X射线晶体结构，并证实了形成的1,2,3-三唑并配体通过中心N2原子配位金属中心。重要的是，确定的具有叠氮基络合物（k_2 = 6.9×10〜（-2）m〜（-1）s〜（-1））的ADIBO环加成反应的二阶速率常数与ADIBO确定的速率相当与有机苄基叠氮化物（k_2 = 4.0×10〜（-1）m〜（-1）s〜（-1）环加成。我们的结果表明，可以将应变促进的叠氮化物-炔烃环加成（SPAAC）的概念从纯有机叠氮化物转移到金属配位的叠氮基配体。 ADIBO-叠氮基-配体环加成反应的良好反应动力学和应变活化炔烃的良好生物正交性应为在生物系统中的应用铺平道路。

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