Asymmetric Disilylation of Spirocyclic Palladacyclopentanes via Tandem Heck/C−H Activation of Aryl Iodides

Abstract The synthesis of chiral organosilicon compounds is highly appealing due to their wide and important applications in synthetic chemistry and medicinal science. However, catalytic asymmetric disilylation are surprisingly underrepresented because of the lack of enantioselective methods in the stereoselective control of silyl group transformations. Herein, an asymmetric palladium‐catalyzed disilylation of ether‐tethered aryl iodide contained a styrene moiety through Heck/C−H activation sequence was explored for the first time. Upon high‐throughput screening of TADDOL‐derived phosphoramidites, it was found that L18 is a good match in combination with Pd(dtbpf)Cl 2 in the tandem Heck/C−H activation of aryl iodide with hexamethyldisilane to afford disilylated 2.3‐dihydrobenzofunan derivatives in good yields with moderate enantioselectivity.