School of Chemistry & Materials Science, Jiangsu Key Laboratory of Green Synthetic Chemistry for Functional Materials , Jiangsu Normal University , Xuzhou 221116 , P. R. China.
Department of Quartermaster and Fuel , Air Force Logistic College , Xuzhou , 221000 , China.
J Org Chem. 2018 Nov 2;83(21):13335-13343. doi: 10.1021/acs.joc.8b02108. Epub 2018 Oct 18.
A new I-mediated iodobenzannulation of yne-allenones has been established, enabling breaking/rearranging of C≡C bonds to selectively access 4-iodonaphthalen-1-ols with generally good yields. The resulting 4-iodonaphthalen-1-ols could serve as a new and reliable coupling reagent, which further reacted with HO under the oxygen conditions to generate unexpected 1,2-carbonyls with good yields through Pd-catalyzed deiodinated carbonylation, whereas employment of benzene-1,2-diamine as the nucleophile rendered 3-(quinoxalin-2-yl)naphthalen-1-ols through Pd-catalyzed [4 + 2] heterocyclization. On the basis of the controlled experiments, the mechanism for forming 1,2-carbonyls was proposed, including an oxidative addition, 1,3-palladium migration, reductive elimination, and oxidative dehydrogenation sequence.
建立了一种新型的 I 介导的炔-烯酮碘苯环化反应，能够选择性地打破/重排 C≡C 键，以通常良好的收率得到 4-碘萘-1-醇。所得的 4-碘萘-1-醇可用作一种新的、可靠的偶联试剂，在氧气条件下进一步与 HO 反应，通过 Pd 催化的脱碘羰基化反应以良好的收率生成意想不到的 1,2-羰基化合物，而苯-1,2-二胺作为亲核试剂通过 Pd 催化的[4 + 2]杂环化反应生成 3-(喹喔啉-2-基)萘-1-醇。根据控制实验，提出了形成 1,2-羰基化合物的机理，包括氧化加成、1,3-钯迁移、还原消除和氧化脱氢序列。
