Photochemical Decarbonylation of Oxetanone and Azetidinone: Spectroscopy, Computational Models, and Synthetic Applications**
Photochemical Decarbonylation of Oxetanone and Azetidinone: Spectroscopy, Computational Models, and Synthetic Applications**
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氧杂环丁酮和氮杂环丁酮的光化学脱羰：光谱学、计算模型和合成应用**
DOI：
10.1002/anie.202215856
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发表时间：
2023
期刊：
影响因子：
--
通讯作者：
Boskovic, Zarko
中科院分区：
文献类型：
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作者：
Singh, Manvendra;Dhote, Pawan;Johnson, Daniel R.;Figueroa‐Lazú, Samuel;Elles, Christopher G.;Boskovic, Zarko
环酮的光激发导致一氧化碳和源自双自由基中间体的产物混合物的排出。在这里，我们表明，如果使用应变杂环酮，则该过程的合成效用会得到改善。 3-氧杂环丁酮和N-Boc-3-氮杂环丁酮的光化学此前从未被描述过。这些四元环的脱羰基是通过 C−C 键从单重激发态逐步诺里什 I 型裂解进行的。衍生自这两种化合物的叶立德是高能物质，其动力学稳定时间足以与各种烯烃进行[3+2]环加成并产生取代的四氢呋喃和吡咯烷。该反应具有足够广泛的范围，可以产生以前无法或难以合成的支架，从而为新的化学空间提供了实验途径。
Photoexcitation of cyclic ketones leads to the expulsion of carbon monoxide and a mixture of products derived from diradical intermediates. Here we show that synthetic utility of this process is improved if strained heterocyclic ketones are used. Photochemistry of 3‐oxetanone andN‐Boc‐3‐azetidinone has not been previously described. Decarbonylation of these 4‐membered rings proceeds through a step‐wise Norrish type I cleavage of the C−C bond from the singlet excited state. Ylides derived from both compounds are high‐energy species that are kinetically stable long enough to undergo [3+2] cycloaddition with a variety of alkenes and produce substituted tetrahydrofurans and pyrrolidines. The reaction has a sufficiently wide scope to produce scaffolds that were either previously inaccessible or difficult to synthesize, thereby providing experimental access to new chemical space.