Asymmetric Hydrovinylation and Hydrogenation with Metal Complexes of C₃‐Symmetric Tris‐Binaphthyl Monophosphites

Abstract

Neutral allyl-palladium complexes stabilised by bulky trisbinaphthyl monophosphite ligands have been prepared and fully characterised in solution by NMR spectroscopy, which evidenced a dynamic equilibrium between two diastereomeric species. The new allyl-palladium phosphite complexes have been evaluated as catalytic precursors in the asymmetric hydrovinylation of styrene; they show moderate activity and good to excellent chemo-and enantioselectivity depending on the substituent at the ligand 2Ј-binaphthyl position. Remarkably, the palladium complex bearing the li-

Computational Exploration of Mechanism and Selectivities of (NHC)Nickel(II)hydride-Catalyzed Hydroalkenylations of Styrene with α-Olefins

“…Hydroalkenylations, which add a vinyl group and a hydrogen across a double bond, are atom and step economic when high reactivity and selectivity is achieved (Scheme ). Since the first report by Alderson in 1965, many research groups have devoted efforts to the development of transition metal catalysts for this reaction. − The phosphorus-based nickel-hydride catalysts and their equivalents, contributed by Wilke, RajanBabu, Leitner, and others, have received the most attention for their high efficiency, chemo- and especially enantioselectivity.…”

Novel Chiral C3-Symmetric Monophosphite Ligands: Synthsis and Catalytic Performance in Asymmetric Hydroformylation and 1,4-Conjugate Addition

“…铑与该系列联 萘酚衍生金刚烷基配体形成的络合物在催化高烯丙醇 底物的不对称氢化中给出 98% ee. 2014 年, Pereira 等 [2] 将此类配体应用于苯乙烯的异烯烃基化中, 获得 92% ee. 到目前为止, 具有螺旋结构的 C 3 对称的单齿亚磷酸 酯配体在不对称氢甲酰化和 1,4-共轭加成反应中的应用 研究尚未有文献报道.…”

Stereoisomeric Tris-BINOL-Menthol Bulky Monophosphites: Synthesis, Characterisation and Application in Rhodium-Catalysed Hydroformylation

“…Moreover, the design and synthesis of chiral phosphite ligands also play a key role in the development of asymmetric catalysis [ 19 , 20 , 21 , 22 ]. Among them, monophosphite ligands based on the binaphthyl backbone [ 23 ] have earned a prominent status due to their synthetic availability and efficient applications in a large number of enantioselective catalytic reactions, namely in hydrogenation [ 24 , 25 , 26 , 27 , 28 ], hydrovinylation [ 29 , 30 ] and allylic substitutions [ 28 , 31 , 32 , 33 , 34 ].…”