Dai Li-Xin, Tu Tao, You Shu-Li, Deng Wei-Ping, Hou Xue-Long
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Lu, Shanghai 200032, China.
Acc Chem Res. 2003 Sep;36(9):659-67. doi: 10.1021/ar020153m.
Chiral ferrocene ligands have been widely used in asymmetric catalysis. The advantages of using ferrocene as a scaffold for chiral ligands are described, particularly those regarding planar chirality, rigid bulkiness, and ease of derivatization. The role of planar chirality in 1,2- and 1,1'-disubstituted ferrocene systems is discussed. By using a bulky ferrocene fragment, novel ferrocene ligands were designed, and high enantioselectivity and regioselectivity were achieved in the allylic substitution reaction of monosubstituted allyl substrates. Using the tunable electronic properties of a diphosphine-oxazoline ferrocenyl ligand, the regioselectivity of the intermolecular asymmetric Heck reaction was also examined.
手性二茂铁配体已广泛应用于不对称催化。本文描述了使用二茂铁作为手性配体骨架的优势，特别是那些与平面手性、刚性体积和易于衍生化相关的优势。讨论了平面手性在1,2 - 和1,1'-二取代二茂铁体系中的作用。通过使用庞大的二茂铁片段，设计了新型二茂铁配体，并在单取代烯丙基底物的烯丙基取代反应中实现了高对映选择性和区域选择性。利用二膦 - 恶唑啉二茂铁基配体的可调电子性质，还研究了分子间不对称Heck反应的区域选择性。
