Selective Arylation and Vinylation at the α Position of Vinylarenes

• Main Authors: Zou, Yinjun, Qin, Liena, Ren, Xinfeng, Lu, Yunpeng, Li, Yongxin, Zhou, Jianrong Steve
• Other Authors: School of Physical and Mathematical Sciences
• Format: Article
• Language: English
• Published: 2014
• Subjects: DRNTU::Science::Chemistry::Organic chemistry::Organometallic compounds
• Online Access: https://hdl.handle.net/10356/102855; http://hdl.handle.net/10220/19097
• Institution: Nanyang Technological University

In intermolecular Heck reactions of styrene and vinylarenes, the aryl and vinyl groups routinely insert at the β position. However, selective insertion at the α position has been very rare. Herein, we provide a missing piece in the palette of Heck reaction, which gave >20:1 α selectivity. The key to our success is a new ferrocene 1,1′-bisphosphane (dnpf) that carries 1-naphthyl groups. Our mechanistic studies revealed that the high α selectivity is partly attributable to the steric effect of dnpf. The rigid and bulky 1-naphthyl groups of dnpf sterically disfavor β insertion.