Applications of Chiral Phosphine‐Based Organocatalysts in Catalytic Asymmetric Reactions

Abstract

Chiral phosphines are versatile Lewis basic catalysts that are capable of promoting a wide range of asymmetric reactions. In particular, recently 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 reactions, cycloaddition reactions, and nucleophilic addition reactions. This short overview summarizes the recent advances in this field and highlights the most-significant achievements.

Asymmetric Dual‐Reagent Catalysis: Mannich‐type Reactions Catalyzed by Ion Pair

“…Over the past decades, chiral organophosphine catalysis [1] has demonstrated high catalytic efficiencies in a range of reactions such as the (aza)Morita-Baylis-Hillman reaction, [2] Rauhut-Currier reaction, [3] Michael (or g) addition reaction, [4] and various annulations. [5] As a general concept, the catalysis and selectivity mediated by nucleophilic phosphine in these reactions have to be initiated by the addition of the phosphine to an electrophilic reactant to form a zwitterion, which then behaves as a key nucleophile or Brønsted base to participate in the catalytic cycle (Scheme 1 a).…”

Convergent Synthesis of Polysubstituted Furans via Catalytic Phosphine Mediated Multicomponent Reactions

“…The troublesome purification of the by-products [5] makes them valueless on an industrial scale [6][7][8]. Also, most well-designed phosphines, especially chiral phosphine reagents [9][10][11][12][13][14][15], are very expensive and high cost hampers their applications in asymmetric Wittig reaction [16][17][18][19][20][21][22][23][24][25]. In this context, it is highly desired to develop a catalytic version of phosphine-mediated Wittig reaction by in-situ recycling by-product phosphine oxide under the aid of a reducing agent.…”

Enantioselective [3 + 2] annulation of α-substituted allenoates with β,γ-unsaturated N-sulfonylimines catalyzed by a bifunctional dipeptide phosphine

“…Over the past decade, chiral phosphine catalysts have been utilized extensively for the construction of a broad range of synthetically useful molecular structures [ 1 – 13 ]. Since the initial discovery of phosphine-catalyzed [3 + 2] annulation of allenoates and activated alkenes by Lu in 1995, this type of annulation reaction has received considerable attention due to its high efficiency and versatility in creating five-membered ring systems [ 14 – 33 ].…”