Cyclic Alkyl Amino Iminate Phosphines: Electron-Rich Ligands with Conformational Potential for C–H···Metal Interactions

Cyclic alkyl amino iminate (CAAI) phosphines were synthesized
in
good yields via chlorophosphine/(CAAI)TMS exchange. These ligands
adopt a conformation in which the methyl groups on the CAAI unit are
oriented toward the metal center, enabling potential weak C–H···metal
interactions, as characterized by experimental and computational methods.
CAAI phosphines have been applied in Pd-catalyzed ketone arylation,
showing promising reactivity with electron-rich substrates. These
findings establish CAAI phosphines as a class of flexible ligand for
transition-metal-catalyzed transformations.

环烷基氨基亚胺基（Cyclic alkyl amino iminate，CAAI）膦可通过氯膦/(CAAI)TMS交换反应以优异收率合成得到。该类配体采取特定构象，其CAAI结构单元上的甲基朝向金属中心，从而可形成潜在的弱C–H···金属相互作用，相关结论经实验与计算方法表征证实。CAAI膦已被应用于钯（Pd）催化的酮芳基化反应中，对富电子底物展现出优异的反应活性。上述研究结果确立CAAI膦为一类适用于过渡金属催化转化反应的柔性配体。