Abstract
Vicinal stereogenic centers represent prevalent structural motifs in organic synthetic
chemistry, and their construction poses a longstanding challenge. Transition-metal-catalyzed
asymmetric allylic substitution has become a well-established enantioselective C–C
bond-forming reaction. When these reactions involve a prochiral nucleophile and an
allylic electrophile with a terminal substituent, the creation of vicinal stereogenic
centers becomes feasible. However, despite remarkable achievements having been accomplished,
realizing this transformation with precise control over both the enantio- and diastereoselectivity
remains a significant challenge. To address the stereoselective challenges, the introduction
of a second catalyst to the transition-metal-catalyzed asymmetric allylic alkylation
to control the diastereoselectivity during C–C bond formation has proven particularly
fruitful. In this short review, we aim to highlight recent advances in dual catalysis
that enable diastereo- and enantioselective allylic substitutions.
1 Introduction
2 Construction of Vicinal Stereogenic Centers by Organo and Metal Dual Catalysis
2.1 Chiral Phase-Transfer Catalysis and Transition-Metal Dual Catalysis
2.2 Chiral Amine and Transition-Metal Dual Catalysis
2.3 NHC and Transition-Metal Dual Catalysis
2.4 Chiral Aldehyde and Transition-Metal Dual Catalysis
2.5 Chiral Lewis Base and Transition-Metal Dual Catalysis
3 Construction of Vicinal Stereogenic Centers by Metal and Metal Dual Catalysis
3.1 Lewis Acidic Metal and Iridium Dual Catalysis
3.2 Lewis Acidic Metal and Palladium Dual Catalysis
3.3 Palladium and Ruthenium Dual Catalysis
3.4 Other Advancements in the Construction of Vicinal Stereogenic Centers through
Synergistic Bimetallic Catalysis Enabling Asymmetric Allylic Alkylation
4 Conclusions and Future Outlook
Key words
transition-metal-catalyzed allylic alkylation - asymmetric allylic substitution -
vicinal stereogenic centers - dual catalysis - synergistic catalysis
