A Gold(I) Complex with a 1,1′-Binaphthyl-Substituted Diphosphene: Synthesis, Structure, and Catalytic Application to Intramolecular Hydroarylation Reactions

A gold­(I) complex with a 1,1′-binaphthyl-substituted diphosphene was synthesized and fully characterized. A phosphorus atom with a less-hindered binaphthyl group coordinates to a gold­(I) moiety in an η1 fashion. Both experiment and theoretical calculations supported the facile rotation around the C­(Naph)–P bond in neutral and cationic diphosphene–gold­(I) complexes. The newly obtained complex 2 was applied to the intramolecular hydroarylation of aryl propynyl ethers 5, and 2H-chromenes 6 were formed in 83–94% yield. Furthermore, the chiral diphosphene–gold­(I) complex (S)-2 was used in the atropselective reaction to furnish 6b,c with up to 9% ee, which is the first example of the use of a diphosphene as a ligand for the transition-metal-catalyzed organic transformation.

合成了一种带有1,1'-联萘取代二磷烯的金(I)配合物，并对其完成了全面表征。位阻更小的联萘基团修饰的磷原子以η1配位模式与金(I)单元配位。实验与理论计算均证实，中性及阳离子型二磷烯-金(I)配合物中，C(萘)-P键可发生快速旋转。将新获得的配合物2应用于芳基炔丙基醚5的分子内氢芳基化反应，以83%~94%的产率得到了2H-色烯6。进一步将手性二磷烯-金(I)配合物(S)-2用于阻转选择性反应，成功获得了对映体过量值（ee）最高达9%的6b、6c，这是二磷烯作为配体应用于过渡金属催化有机转化反应的首例。