Asymmetric α-allylic allenylation of β-ketocarbonyls and aldehydes by synergistic Pd/chiral primary amine catalysis

You, Chang; Shi, Mingying; Mi, Xueling; Luo, Sanzhong

doi:10.1038/s41467-023-38488-4

Cited by 25 publications

(10 citation statements)

References 54 publications

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“…25 Most recently, they successfully extended the synergistic primary amine 29 or 30/Pd-L5 or L6 system to stereodivergent α-allenylic alkylation of both branched aldehydes and β-keto esters 26 using 1,3-enynes 27 as π-allenyl-Pd precursors (Scheme 9). 26 The reaction provides a highly stereoselective manner for the construction of all-carbon quaternary centertethered allenes bearing a nonadjacent 1,3-axial-central chirality, which is otherwise inaccessible with conventional strategies.…”

Section: Dual Organo/metal Catalysismentioning

confidence: 99%

Synergistic Dual Catalysis in Stereodivergent Synthesis

Wei,

Fu,

Wang

et al. 2024

ACS Catal.

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Chiral skeletons with multiple stereogenic centers widely reside in nature and drugs, and their relative and absolute configuration often determine their physiological or pharmacological properties. Stereodivergent synthesis of chiral molecules is not only of great significance, but also is highly challenging since the formation of one of the diastereomers is inherently preferred in most asymmetric reactions. Stereodivergent dual catalysis, introduced in 2013 by the Carreira group, perfectly catered to all the requirements for full stereoselectivity control of given reactions since two chiral catalysts are utilized in a synergistic way and act independently, and has now been arguably the most efficient strategy to realize stereodivergent synthesis. This comprehensive review presents an overview of the development of stereodivergent synthesis enabled by synergistic dual catalysis in the past ten years, providing readers with the fundamental attributes as well as the ability, scope, mechanism, as well as limitations of this strategy.

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Section: Dual Organo/metal Catalysismentioning

confidence: 99%

Synergistic Dual Catalysis in Stereodivergent Synthesis

Wei,

Fu,

Wang

et al. 2024

ACS Catal.

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“…The construction of nonadjacent 1,3-central axial chirality remains a great challenge in asymmetric catalysis . 1,3-Conjugated enynes could be successfully applied in the chiral primary amine/Pd synergistic catalysis to deliver chiral allenes 3 with high diastereo- and enantioselectivity featuring effective control of nonadjacent central and axial stereoselectivity (Scheme III).…”

Section: Synergistic Catalysis With Transition Metalmentioning

confidence: 99%

Enantioselective Transformations by “1 + x” Synergistic Catalysis with Chiral Primary Amines

Cai,

Zhang,

Zhang

et al. 2024

Acc. Chem. Res.

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Metrics & MoreArticle Recommendations CONSPECTUS: Synergistic catalysis is a powerful tool that involves two or more distinctive catalytic systems to activate reaction partners simultaneously, thereby expanding the reactivity space of individual catalysis. As an established catalytic strategy, organocatalysis has found numerous applications in enantioselective transformations under rather mild conditions.Recently, the introduction of other catalytic systems has significantly expanded the reaction space of typical organocatalysis. In this regard, aminocatalysis is a prototypical example of synergistic catalysis. The combination of aminocatalyst and transition metal could be traced back to the early days of organocatalysis and has now been well explored as an enabling catalytic strategy. Particularly, the acid−base properties of aminocatalysis can be significantly expanded to include usually electrophiles generated in situ via metal-catalyzed cycles. Later on, aminocatalyst has also been exploited in synergistically combining with photochemical and electrochemical processes to facilitate redox transformations. However, synergistically combining one type of aminocatalyst with many different catalytic systems remains a great challenge. One of the most daunting challenges is the compatibility of aminocatalysts in coexistence with other catalytic species. As nucleophilic species, aminocatalysts may also bind with metal, which leads to mutual inhibition or even quenching of the individual catalytic activity. In addition, oxidative stability of aminocatalyst is also a nonneglectable issue, which causes difficulties in exploring oxidative enamine transformations.In 2007, we developed a vicinal diamine type of chiral primary aminocatalysts. This class of primary aminocatalysts was developed and evolved as functional and mechanistic mimics to the natural aldolase and has been widely applied in a number of enamine/ iminium ion-based transformations. By following a "1 + x" synergistic strategy, the chiral primary amine catalysts were found to work synergistically or cooperatively with a number of transition metal catalysts, such as Pd, Rh, Ag, Co, and Cu, or other organocatalysts, such as B(C 6 F 5 ) 3 , ketone, selenium, and iodide. Photocatalysis and electrochemical processes can also be incorporated to work together with the chiral primary amine catalysts. The 1 + x catalytic strategy enabled us to execute unexploited transformations by fine-tuning the acid−base and redox properties of the enamine intermediates and to achieve effective reaction and stereocontrol beyond the reach individually. During these efforts, an unprecedented excited-state chemistry of enamine was uncovered to make possible an effective deracemization process. In this Account, we describe our recent efforts since 2015 in exploring synergistic chiral primary amine catalysis, and the content is categorized according to the type of synergistic partner such that in each section the developed synergistic catalysis, reaction scopes, and mechanistic features...

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“…Despite these significant advances, creating quaternary stereocenters asymmetrically via iron-catalyzed outer-sphere alkyl–alkyl cross-coupling, particularly with unactivated alkyl sources, remains a challenge. Drawing upon the seminal work on ternary catalysis by Luo and co-workers, , we propose a photoredox/Fe/chiral primary amine triple catalysis scheme for a novel approach to generating quaternary stereocenters with enantiocontrol (Figure D). Notably, enantioselective organocatalysis was recognized as one of the ten emerging technologies in chemistry with the potential to make our planet more sustainable by IUPAC on its 100th anniversary in 2019 .…”

Section: Introductionmentioning

confidence: 99%

Enantioselective Construction of Quaternary Stereocenters via Cooperative Photoredox/Fe/Chiral Primary Amine Triple Catalysis

Li,

Zhang,

et al. 2024

J. Am. Chem. Soc.

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The catalytic and enantioselective construction of quaternary (all-carbon substituents) stereocenters poses a formidable challenge in organic synthesis due to the hindrance caused by steric factors. One conceptually viable and potentially versatile approach is the coupling of a C−C bond through an outer-sphere mechanism, accompanied by the realization of enantiocontrol through cooperative catalysis; however, examples of such processes are yet to be identified. Herein, we present such a method for creating different compounds with quaternary stereocenters by photoredox/Fe/chiral primary amine triple catalysis. This approach facilitates the connection of an unactivated alkyl source with a tertiary alkyl moiety, which is also rare. The scalable process exhibits mild conditions, does not necessitate the use of a base, and possesses a good functional-group tolerance. Preliminary investigations into the underlying mechanisms have provided valuable insights into the reaction pathway.

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Asymmetric α-allylic allenylation of β-ketocarbonyls and aldehydes by synergistic Pd/chiral primary amine catalysis

Cited by 25 publications

References 54 publications

Synergistic Dual Catalysis in Stereodivergent Synthesis

Synergistic Dual Catalysis in Stereodivergent Synthesis

Enantioselective Transformations by “1 + x” Synergistic Catalysis with Chiral Primary Amines

Enantioselective Construction of Quaternary Stereocenters via Cooperative Photoredox/Fe/Chiral Primary Amine Triple Catalysis

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