Phosphine Organocatalysis for the Synthesis of Spirocyclic Compounds

Abstract

This account describes the use of phosphines as simple organocatalysts that catalyze the synthesis of complex spirocyclic compounds. Besides our own results, coverage of relevant literature in this field is also provided, including asymmetric variants and synthetic applications. Cycloaddition Reactions Using Ynone Derivatives 5 Cycloaddition Reactions Involving Methyl Vinyl Ketone Derivatives 6 Miscellaneous Reactions 7 Conclusions

Inhibition of p53-Murine Double Minute 2 (MDM2) Interactions with 3,3′-Spirocyclopentene Oxindole Derivatives

“…For building the spirocyclic scaffold of 4 , we take advantage of the so-called Lu’s reaction, a phosphine promoted [3 + 2] cyclization between electron-poor allenes and electron-poor olefins leading to highly functionalized cyclopentenes. , We and others have demonstrated previously that this general method can be conveniently applied to the cyclization between 3-arylidene oxindoles I and allenoates II to afford spirooxindole derivatives III or IV in racemic and enantioenriched forms (Figure ). − Starting from nonsubstituted allenoates (R′ = H), the reaction affords spirooxindoles III . With γ-substituted allenoates (R′ ≠ H) the reaction takes place regioselectively via α-addition of the allenoate–phosphine zwitterionic adduct and ends up with spirocyclopent-3-enes IV .…”

Asymmetric Construction of Highly Functionalized Spirobarbiturate‐Cyclopentenes through Chiral Phosphine‐Catalyzed [3+2] Annulation of Morita–Baylis–Hillman Carbonates with Barbiturate‐Derived Alkenes

“…Phosphine‐catalyzed annulation reactions are very powerful methods in the syntheses of carbocyclic and heterocyclic compounds and serve as the key step in the total synthesis of some natural products . Particularly, these annulations have also successfully been applied in the synthesis of complex spirocyclic compounds . Among various annulation reactions, the phosphine‐catalyzed [3+2] annulation reaction of MBH carbonates with olefins has emerged as an important tool to synthesize cyclopentenes since Lu first reported a phosphine‐catalyzed [3+2] annulation of MBH carbonates as a three‐carbon synthon with electron‐deficient alkenes ,.…”

Phosphine-Catalyzed Asymmetric Organic Reactions

“…Since then, it is the past decade that has observed numerous significant advances that asymmetric phosphine catalysis has become a common tool in asymmetric synthesis. A good number of excellent reviews and accounts on phosphine catalysis have been published, especially in recent years. − However, to give impetus to this fascinating field, an updated and comprehensive review on asymmetric phosphine catalysis is still highly desirable. In this review, we compile exhaustively the chiral phosphine-catalyzed asymmetric organic reactions in the literature, from late 1990s all the way to the end of 2017, and attempt to provide a critical, panoramic picture, as well as an outlook of this dynamic research field.…”