Asymmetric Disilylation of Spirocyclic Palladacyclopentanes via Tandem Heck/C−H Activation of Aryl Iodides. Issue 11 (6th October 2021)

• Record Type: Journal Article
• Authors: Li, Hang; Huang, Wei‐Sheng; Yang, Ke‐Fang; Ye, Fei; Yin, Guan‐Wu; Xu, Zheng; Xu, Li‐Wen
• Is Part Of: Asian journal of organic chemistry. Volume 10:Issue 11(2021)
• Page Start: 2883
• Page End: 2887
• Publication Date: 2021-10-06
• Subjects: Organosilicon -- palladium -- disilylation -- spirocycle -- chiral ligand; Chemistry, Organic -- Periodicals; Organic compounds -- Synthesis -- Periodicals; 547.005
• DOI: 10.1002/ajoc.202100502
• Languages: English
• ISSNs: 2193-5807

Abstract

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)Cl2 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. Abstract : A TADDOL‐derived phosphoramidite ligand was found to be a good match in combination with Pd(dtbpf)Cl2 in the palladium‐catalyzed tandem Heck/C−H activation of aryl iodide with hexamethyldisilane to afford disilylated 2, 3‐dihydrobenzofunan derivatives in good yields with moderated enantioselectivity.