Polar-Radical Cyclization Cascades with Magnesiated Nitriles
Polar-Radical Cyclization Cascades with Magnesiated Nitriles
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DOI：
10.1021/acs.orglett.3c01094
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发表时间：
2023-05-04
期刊：
影响因子：
5.2
通讯作者：
Fleming，Fraser F.
中科院分区：
文献类型：
--
作者：
Bolgunas，Stephen;Paleo，Ehecatl;Fleming，Fraser F.
萘通过极性-自由基加成-环化级联反应将磁化的ω-烯基腈转化为双环酮和三环酮。氧化镁腈的单电子氧化生成了腈稳定的自由基，这些自由基环化到侧链烯烃上，然后通过还原-环化序列反弹到丁腈上；随后的水解得到了各种不同的双环[3.2.0]庚烷-6-酮。将极性-自由基级联反应与1，2：1，4-羰基共轭加成反应相结合，在一次合成操作中合成了含有四个新碳-碳键和四个手性中心的复杂环丁酮。
Naphthalene converts magnesiated ω-alkenylnitriles into bi- and tricyclic ketones via a polar-radical addition–cyclization cascade. One-electron oxidation of magnesiated nitriles generates nitrile-stabilized radicals that cyclize onto a pendant olefin and then rebound onto the nitrile through a reduction–cyclization sequence; subsequent hydrolysis affords a diverse array of bicyclo[3.2.0]heptan-6-ones. Combining the polar-radical cascade with a 1,2:1,4-carbonyl-conjugate addition generates complex cyclobutanones containing four new carbon–carbon bonds and four chiral centers in one synthetic operation.