Quirós Irene, Martín María, Gomez-Mendoza Miguel, Cabrera-Afonso María Jesús, Liras Marta, Fernández Israel, Nóvoa Luis, Tortosa Mariola
Organic Chemistry Department, Universidad Autónoma de Madrid (UAM), Avda. Francisco Tomás y Valiente 7, Cantoblanco, 28049, Madrid, Spain.
Photoactivated Processes Unit, IMDEA Energy, Av. Ramón de la Sagra 3, Móstoles, 28935, Madrid, Spain.
Angew Chem Int Ed Engl. 2024 Feb 12;63(7):e202317683. doi: 10.1002/anie.202317683. Epub 2024 Jan 12.
Herein, we report the use of isonitriles as alkyl radical precursors in light-mediated hydro- and deuterodeamination reactions. The reaction is scalable, shows broad functional group compatibility and potential to be used in late-stage functionalization. Importantly, the method is general for C -primary, C -secondary and C -tertiary alkyl isonitriles. For most examples, high yields were obtained through direct visible-light irradiation of the isonitrile in the presence of a silyl radical precursor. Interestingly, in the presence of an organic photocatalyst (4CzIPN) a dramatic acceleration was observed. In-depth mechanistic studies using UV/Vis absorption, steady-state and time-resolved photoluminescence, and transient absorption spectroscopy suggest that the excited state of 4CzIPN can engage in a single-electron transfer with the isonitrile.
在此，我们报道了异腈在光介导的氢脱氨基和氘代脱氨基反应中作为烷基自由基前体的应用。该反应具有可扩展性，显示出广泛的官能团兼容性以及在后期官能化中应用的潜力。重要的是，该方法对伯碳、仲碳和叔碳烷基异腈均适用。对于大多数实例，通过在硅基自由基前体存在下直接可见光照射异腈可获得高产率。有趣的是，在有机光催化剂（4CzIPN）存在下观察到了显著的加速。使用紫外/可见吸收、稳态和时间分辨光致发光以及瞬态吸收光谱进行的深入机理研究表明，4CzIPN的激发态可与异腈发生单电子转移。
