Gao Xin-Yu, Tang Lei, Zhang Xu, Feng Jian-Jun
State Key Laboratory of Chemo/Biosensing and Chemometrics, Advanced Catalytic Engineering Research Center of the Ministry of Education, College of Chemistry and Chemical Engineering, Hunan University Changsha Hunan 410082 P. R. China
School of Chemistry & Chemical Engineering, Yangzhou University Yangzhou 225002 P.R. China.
Chem Sci. 2024 Aug 6;15(34):13942-8. doi: 10.1039/d4sc02998d.
While cycloaddition reactions of bicyclobutanes (BCBs) have emerged as a potent method for synthesizing (hetero-)bicyclo[.1.1]alkanes (usually ≤ 3), their utilization in the synthesis of bicyclo[4.1.1]octane derivatives (BCOs) is still underdeveloped. Here, a palladium-catalyzed formal (4 + 3) reaction of BCBs with 1,4-O/C dipole precursors for the synthesis of oxa-BCOs is described. Unlike previous catalytic polar (3 + X) cycloadditions of BCBs, which are typically achieved through the activation of BCB substrates, the current reaction represents a novel strategy for realizing the cycloaddition of BCBs through the activation of the "X" cycloaddition partner. Moreover, the obtained functionalized oxa-BCOs products can be readily modified through various synthetic transformations.
虽然双环丁烷（BCBs）的环加成反应已成为合成（杂）双环[1.1.1]烷烃（通常≤3）的有效方法，但其在双环[4.1.1]辛烷衍生物（BCOs）合成中的应用仍未得到充分发展。在此，描述了一种钯催化的BCBs与1,4-O/C偶极前体的形式（4 + 3）反应，用于合成氧杂-BCOs。与之前通过激活BCB底物实现的BCBs催化极性（3 + X）环加成不同，当前反应代表了一种通过激活“X”环加成伙伴来实现BCBs环加成的新策略。此外，所得到的功能化氧杂-BCOs产物可以通过各种合成转化轻松进行修饰。
