Zhang Xiang-Xin, Zheng Hao, Mei Yong-Kang, Liu Yan, Liu Ying-Ying, Ji Ding-Wei, Wan Boshun, Chen Qing-An
Dalian Institute of Chemical Physics, Chinese Academy of Sciences Dalian 116023 People's Republic of China.
University of Chinese Academy of Sciences Beijing 100049 People's Republic of China
Chem Sci. 2023 Sep 25;14(40):11170-11179. doi: 10.1039/d3sc03667g. eCollection 2023 Oct 18.
A catalyst-free photosensitized strategy has been developed for regioselective imino functionalizations of alkenes the formation of an EDA complex. This photo-induced protocol facilitates the construction of structurally diverse β-imino sulfones and vinyl sulfones in moderate to high yields. Mechanistic studies reveal that the reaction is initiated with an intermolecular charge transfer between oximes and sulfinates, followed by fragmentation to generate a persistent iminyl radical and transient sulfonyl radical. This catalyst-free protocol also features excellent regioselectivity, broad functional group tolerance and mild reaction conditions. The late stage functionalization of natural product derived compounds and total synthesis of some bioactive molecules have been demonstrated to highlight the utility of this protocol. Meanwhile, the compatibility of different donors has proved the generality of this strategy.
已开发出一种无催化剂的光敏策略，用于烯烃的区域选择性亚氨基官能化——形成电子给体-受体（EDA）复合物。这种光诱导方案有助于以中等到高的产率构建结构多样的β-亚氨基砜和乙烯基砜。机理研究表明，反应始于肟和亚磺酸盐之间的分子间电荷转移，随后发生碎片化以产生持久的亚氨自由基和瞬态磺酰基自由基。这种无催化剂方案还具有出色的区域选择性、广泛的官能团耐受性和温和的反应条件。天然产物衍生化合物的后期官能化以及一些生物活性分子的全合成已得到证明，以突出该方案的实用性。同时，不同供体的兼容性证明了该策略的通用性。
