Asymmetric Reactions Catalyzed by Chiral Tertiary Phosphines

Abstract

Chiral tertiary phosphines are versatile Lewis base catalysts capable of promoting a wide range of asymmetric reactions. In particular, the recent designed chiral phosphines based on the concept of bi-/multifunctionality have been demonstrated to be effective catalysts for many types of asymmetric reactions such as (aza)-MBH reaction/RC reaction, cycloaddition reaction, domino reaction, nucleophilic addition reaction, etc. This review summarizes the recent advances in this field and highlights the selected significant achievements. Dr. Yin Wei (left) received her PhD from Ludwig-Maximilians-Universität in München (Germany) in 2009 under the direction of Professor Hendrik Zipse. Subsequently, she joined in Professor Min Shi's group at Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences (SIOC, CAS), and was promoted as an associate professor in 2012. She has authored over 100 scientific publications, and she is mainly working on the theoretical studies of organocatalysis.

Trivalent Phosphine‐Catalyzed Reactions Using Fluorinated Building Blocks

“…In addition, the easy controlling of steric, electronic, and nucleophilic properties of phosphines helps to achieve desired chemo-, regio-and stereoselectivities, which makes them promising catalyst candidates. [9] On the other hand, the judicious introduction of fluorine atom/s or fluoroalkyl group/s into organic frameworks has profound effect on the physiochemical and biological properties of parent molecules. [10] Such modification increases the possibility of H-bonding interaction, alters the conformational flexibility, affects the pK a value of neighbouring functional groups to name a few, which can boost the metabolic stability, lipophilicity, bioavailability, and permeability of resulting molecules.…”

Manganese(I)-Catalyzed Asymmetric Hydrophosphination of α,β-Unsaturated Carbonyl Derivatives

“…Phosphines containing carbon stereocenters make up an important class of compounds that have found applications in asymmetric catalysis, both as ligands, in combination with various transition metals, and in their own right as chiral organocatalysts. , These phosphines are often difficult to access, due to their laborious, multistep synthesis, and therefore are expensive. In addition, their preparation commonly requires stoichiometric amounts of chiral auxiliaries or performing optical resolutions of preformed racemates .…”

Effects of Anchimeric Assistance in Phosphonium Enolates Chemistry

“…Such intermediates are highly reactive and can be involved into a large number of catalytic transformations with electrophilic partners of various nature with the elimination of phosphine at the final step of the catalytic cycle, which is generally shown in Scheme 1. Phosphine-catalyzed reactions (Morita-Baylis-Hillman, Rauhut-Currier, Michael, [3+2]-and [4+2]-cycloaddition of activated allenes to alkenes and imines, α-and γ-umpolung addition of nucleophiles to activated alkynes and allenes) have become convenient tools in modern organic synthesis to produce compounds with a new carbon-carbon and carbon-heteroatom bond (Scheme 2) [1][2][3][4][5][6].…”