Stereodivergent Desymmetrization of Simple Dicarboxylates via Branch‐Selective Pd/Cu Catalyzed Allylic Substitution

Li, Guanlin; Zhao, Ling; Luo, Yicong; Peng, Youbin; Xu, Kai; Huo, Xiaohong; Zhang, Wanbin

doi:10.1002/chem.202200273

Cited by 7 publications

(1 citation statement)

References 160 publications

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“…However, expanding the scope of the electrophile remains unaddressed. 42,49 Scheme 17 Asymmetric allylation of -CF 3 -azaindolineacetamides facilitated by copper and palladium dual catalysis…”

Section: Lewis Acidic Metal and Palladium Dual Catalysismentioning

confidence: 99%

Dual-Catalysis-Enabled Construction of Vicinal Stereogenic Centers through Diastereo- and Enantioselective Allylic Substitution

Su,

Yang,

Chen

2024

Synthesis

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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 Introduction2 Construction of Vicinal Stereogenic Centers by Organo and Metal Dual Catalysis2.1 Chiral Phase-Transfer Catalysis and Transition-Metal Dual Catalysis2.2 Chiral Amine and Transition-Metal Dual Catalysis2.3 NHC and Transition-Metal Dual Catalysis2.4 Chiral Aldehyde and Transition-Metal Dual Catalysis2.5 Chiral Lewis Base and Transition-Metal Dual Catalysis3 Construction of Vicinal Stereogenic Centers by Metal and Metal Dual Catalysis3.1 Lewis Acidic Metal and Iridium Dual Catalysis3.2 Lewis Acidic Metal and Palladium Dual Catalysis3.3 Palladium and Ruthenium Dual Catalysis3.4 Other Advancements in the Construction of Vicinal Stereogenic Centers through Synergistic Bimetallic Catalysis Enabling Asymmetric Allylic Alkylation4 Conclusions and Future Outlook

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Section: Lewis Acidic Metal and Palladium Dual Catalysismentioning

confidence: 99%

Dual-Catalysis-Enabled Construction of Vicinal Stereogenic Centers through Diastereo- and Enantioselective Allylic Substitution

Su,

Yang,

Chen

2024

Synthesis

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Pd/Cu Catalyzed Asymmetric Allylation for Stereodivergent Synthesis of Glutamic Acid Derivatives

Li,

Liu,

Han

et al. 2024

Chemistry A European J

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A synergistic Pd/Cu catalyst system has been developed for stereodivergent transformation of Morita‐Baylis‐Hillman (MBH) carbonates and Schiff bases derived from simple amino acids to afford a series of optically active β‐branched γ‐methyleneglutamic acid derivatives with adjacent tertiary/tertiary and quaternary/tertiary stereocenters in high yields (up to 96%) with excellent diastereo‐ and enantioselectivities (>20/1 dr and >99% ee in most cases) under mild conditions. The use of SKP ligand is disclosed to be crucial for the success of the transformation, and in particular allowing the reaction to proceed at low catalyst loading (0.02 mol% for Pd and 0.08 mol% for Cu). The high efficiency of the catalysis was attributed to the formation of intimate ion pair complex A1, composed of Pd‐phosphonium cation and a t‐butoxide anion, which would facilitate the subsequent deprotonation and C‐C coupling events. All four stereoisomers of the β‐branched glutamic acid derivatives were readily prepared by permutation of the catalyst enantiomers. Synthetic utility of the methodology was exemplified by efficient synthesis of a fused pyrrolooxazolidinone with three contiguous chiral centers, highlighting the power of synergistic Pd/Cu catalysis for asymmetric allylic alkylation with MBH carbonates.

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Asymmetric Synthesis of Anti‐tuberculosis‐specific Drug TBAJ‐876 through Synergistic Li/Li Catalysis

Gao

Ahmad

et al. 2023

Chin. J. Chem.

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Comprehensive Summary TBAJ‐876, developed by TB Alliance, a novel anti‐tuberculosis‐specific drug, has entered Phase II clinical trials. Herein, the first asymmetric synthesis of TBAJ‐876 has been realized using synergistic Li/Li catalysis with excellent yield of 95% and 88 : 12 er (99.6 : 0.4 er, 10 : 1 dr after simple recrystallization). Furthermore, DFT calculations and 7Li‐NMR analysis illustrated the mechanism of the synergistic reaction: a chiral Li‐complex activates the nucleophile to control the stereoselectivity, while the other achiral Li‐complex activates the electrophile to catalyze the carbonyl addition reaction. Additionally, this protocol has been successfully carried out at 5 gram‐scale, showing its industrial potential.

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Stereodivergent Desymmetrization of Simple Dicarboxylates via Branch‐Selective Pd/Cu Catalyzed Allylic Substitution

Cited by 7 publications

References 160 publications

Dual-Catalysis-Enabled Construction of Vicinal Stereogenic Centers through Diastereo- and Enantioselective Allylic Substitution

Dual-Catalysis-Enabled Construction of Vicinal Stereogenic Centers through Diastereo- and Enantioselective Allylic Substitution

Pd/Cu Catalyzed Asymmetric Allylation for Stereodivergent Synthesis of Glutamic Acid Derivatives

Asymmetric Synthesis of Anti‐tuberculosis‐specific Drug TBAJ‐876 through Synergistic Li/Li Catalysis

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