Recent progress in asymmetric synergistic catalysis – the judicious combination of selected chiral aminocatalysts with achiral metal catalysts

Nielsen, Christian D.-T.; Linfoot, Joshua D; Williams, Alexander F.; Spivey, Alan C.

doi:10.1039/d2ob00025c

Cited by 17 publications

(9 citation statements)

References 86 publications

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“…116,117 In addition, integrating the photochemical activity of chiral organocatalytic intermediates within metal-mediated catalytic cycles may also enable unconventional mechanisms for stereocontrolled bond formation. 118 6.3. Late-Stage Functionalization.…”

Section: Stereochemistry and Isomerizationmentioning

confidence: 99%

“…New research findings have also shown that by using light to excite chiral organocatalytic intermediates, novel catalytic functions can be activated, thus enabling the synthesis of chiral molecules that would otherwise be challenging to obtain using conventional ground-state reactivity. Therefore, the photochemistry of organocatalytic intermediates can open up new synthetic possibilities, expanding the scope of organocatalysis to encompass radical chemistry and excited-state reactivity. , In addition, integrating the photochemical activity of chiral organocatalytic intermediates within metal-mediated catalytic cycles may also enable unconventional mechanisms for stereocontrolled bond formation …”

Section: Hit-to-lead and Lead Optimizationmentioning

confidence: 99%

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Photochemistry in Medicinal Chemistry and Chemical Biology

Zhu,

Empel,

Pelliccia

et al. 2024

J. Med. Chem.

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Photochemistry has emerged as a transformative force in organic chemistry, significantly expanding the chemical space accessible for medicinal chemistry. Light-induced reactions enable the efficient synthesis of intricate organic structures and have found applications throughout the different stages of the drug discovery and development processes. Moreover, photochemical techniques provide innovative solutions in chemical biology, allowing precise spatiotemporal drug activation and targeted delivery. In this Perspective, we highlight the already numerous remarkable applications and the even more promising future of photochemistry in medicinal chemistry and chemical biology. ■ SIGNIFICANCE• Medicinal chemistry and chemical biology can highly benefit from the recent developments in the field of photochemistry in organic synthesis. • The most relevant applications of photochemistry and photocatalysis in the different stages of the drug discovery process have been highlighted. • With this Perspective, we would like to point out the potential and challenges of photochemistry in chemical biology applications.

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Section: Stereochemistry and Isomerizationmentioning

confidence: 99%

Section: Hit-to-lead and Lead Optimizationmentioning

confidence: 99%

Photochemistry in Medicinal Chemistry and Chemical Biology

Zhu,

Empel,

Pelliccia

et al. 2024

J. Med. Chem.

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“…The integration of organocatalysis and transition-metal catalysis is increasingly recognized as a potent strategy 5a f h 7 for creating vicinal stereogenic centers via nucleophilic allylic substitution reactions. Organocatalysts, 7,8 including chiral phase-transfer reagents, amines, aldehydes, N -heterocyclic carbenes (NHCs), and Lewis bases, are commonly employed to activate the pre-nucleophiles, and transition-metal catalysts, notably palladium and iridium, are utilized to activate allylic electrophiles.…”

Section: Construction Of Vicinal Stereogenic Centers By Organo and Me...mentioning

confidence: 99%

“…4c,d To utilize these less reactive carbonyl compounds in catalytic asymmetric allylic substitution, they often require stoichiometric pre-activation into the corresponding metal enolates, silyl enol ethers, or enamines. 4c Chiral amine and transition-metal dual catalysis 5a c h has been instrumental in broadening the range of enolate nucleophiles in catalytic asymmetric allylic allylation processes.…”

Section: Construction Of Vicinal Stereogenic Centers By Organo and Me...mentioning

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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“…Synergistic metal–organo catalysis has flourished into a highly significant and useful strategy in chemical synthesis, where the complementary modes of substrate activation would bring about novel types of transformations or improve the efficiency and chemo-, regio-, and stereoselectivities of known reactions . In this context, the combination of a transition metal and primary or secondary amine catalysts has attracted considerable attention from synthetic chemists, who merged enamine catalysis with several modes of electrophile activation with transition-metal catalysts for carbonyl α-functionalizations, such as α-allylation and -alkylation reactions .…”

mentioning

confidence: 99%

Skeletal Transformation of Oxindoles into Quinolinones Enabled by Synergistic Copper/Iminium Catalysis

et al. 2023

J. Org. Chem.

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We describe a synergistic Cu/secondary amine catalysis for skeletal transformation of an oxindole core into a quinolinone skeleton, which generates several structurally new pyridine-fused quinolinones. The synergistic reactions allow expansion of a five-membered lactam ring by radical cation-triggered C–C bond cleavage and enable a further intramolecular cyclization with the aim to construct totally distinct core skeletons.

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Recent progress in asymmetric synergistic catalysis – the judicious combination of selected chiral aminocatalysts with achiral metal catalysts

Abstract: In this review we survey the most recent synergistic applications of a chiral organocatalyst with an achiral metal to perform stereoselective transformations of synthetic utility (since 2016). The transformations are...

Cited by 17 publications

References 86 publications

Photochemistry in Medicinal Chemistry and Chemical Biology

Photochemistry in Medicinal Chemistry and Chemical Biology

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

Skeletal Transformation of Oxindoles into Quinolinones Enabled by Synergistic Copper/Iminium Catalysis

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