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 410082, P. R. China.
The Institute of Scientific and Industrial Research, Osaka University, 8-1 Mihogaoka, Ibaraki-shi, Osaka 567-0047, Japan.
J Org Chem. 2022 Jun 17;87(12):7720-7733. doi: 10.1021/acs.joc.2c00308. Epub 2022 May 27.
RPCFH ligands and their RP(O)CFH precursors were synthesized from RP(O)H with TMSCF by simply modulating the HO concentration via deoxydifluoromethylation and difluoromethylation. The air sensitive RPCFH phosphines can be stabilized in Cu(I) clusters as ligands. Within these Cu(I) clusters, the Sonogashira cross-coupling reaction can proceed fast and efficiently using terminal alkynes and aryl iodides within 15 min at room temperature under air to give a variety of diaryl(alkyl)acetylenes in good yields (49 examples, yields of ≤99%). Six of the internal alkynes present in drug precursors can be obtained using this protocol in good yields. The mechanism is proposed on the basis of control experiments.
通过去氧二氟甲基化和二氟甲基化反应，简单地通过调节 HO 浓度，从 RP(O)H 用 TMSCF 合成 RPCFH 配体及其 RP(O)CFH 前体。空气敏感的 RPCFH 膦配体可以在 Cu(I)簇中作为配体稳定下来。在这些 Cu(I)簇中，末端炔烃和芳基碘化物可以在室温下、空气中快速有效地进行 Sonogashira 交叉偶联反应，在 15 分钟内以良好的收率（49 个实例，收率≤99%）得到各种二芳基（烷基）乙炔。该方案可以以良好的收率得到药物前体中存在的 6 个内部炔烃。该机理是基于对照实验提出的。
