Catalytic Asymmetric Oxidative γ‐Coupling of α,β‐Unsaturated Aldehydes with Air as the Terminal Oxidant

Næsborg, Line; Corti, Vasco; Leth, Lars A.; Poulsen, Pernille; Jørgensen, Karl Anker

doi:10.1002/anie.201711944

Cited by 36 publications

(18 citation statements)

References 47 publications

(8 reference statements)

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“…Recently, we reported that α,β‐unsaturated aldehydes undergo stereoselective γ‐couplings in the presence of Cu II , an aminocatalyst, and air (O 2 ) as terminal oxidant . When testing linear aldehydes under these conditions, a product containing a carbon‐carbon double bond connecting the two aldehydes was obtained.…”

Section: Resultssupporting

confidence: 87%

Direct Enantio‐ and Diastereoselective Oxidative Homocoupling of Aldehydes

Næsborg

Leth

Reyes‐Rodríguez

et al. 2018

Chemistry A European J

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A novel strategy for the direct enantioselective oxidative homocoupling of α-branched aldehydes is presented. The methodology employs open-shell intermediates for the construction of chiral 1,4-dialdehydes by forming a carbon-carbon bond connecting two quaternary stereogenic centers in good yields and excellent stereoselectivities for electron-rich aromatic aldehydes. The 1,4-dialdehydes were transformed into synthetically valuable chiral pyrrolidines. Experimental mechanistic investigations based on competition experiments combined with computational studies indicate that the reaction proceeds through a radical cation intermediate and that reactivity and stereoselectivity follow different trends.

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Section: Resultssupporting

confidence: 87%

Direct Enantio‐ and Diastereoselective Oxidative Homocoupling of Aldehydes

Næsborg

Leth

Reyes‐Rodríguez

et al. 2018

Chemistry A European J

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“…Recently, radical type asymmetric C(sp 3 )–H alkylations have received more and more attention. To achieve enantioselectivities, the reported alkylative coupling partners were structurally limited, in which coordinatable atoms or functional groups, such as heteroatoms (S, O, N, and et al) or π-electron contained groups (alkene, alkyne, carbonyl, and et al) were essentially required to deliver chirality from chiral catalysts. − In contrast, the asymmetric sp 3 C–H alkylations with simply unbiased alkyl fragments, such as n -butyl, cyclohexyl, t-butyl, and et al were not realized and still highly desired.…”

Section: Introductionmentioning

confidence: 99%

Visible Light Induced Cu-Catalyzed Asymmetric C(sp³)–H Alkylation

Wang

Huo

et al. 2021

J. Am. Chem. Soc.

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The asymmetric functionalization of C–H is one of the most attractive strategies in asymmetric synthesis. In the past decades, catalytic enantioselective C(sp3)–H functionalization has been intensively studied and successfully applied in various asymmetric bond formations, whereas asymmetric C(sp3)–H alkylation was not well developed. Photoredox catalysis has recently emerged as an efficient way to synthesize organic compounds under mild conditions. Despite many photoinduced stereoselective reactions that have been achieved, the related enantioselective C(sp3)–C(sp3) coupling is challenging, especially of the photocatalytic asymmetric C(sp3)–H radical alkylation. Here, we report a visible light induced Cu catalyzed asymmetric sp 3 C–H alkylation, which is effective for coupling with unbiased primary, secondary, and tertiary alkyl fragments in high enantioselectivities. This reaction would provide a new approach for the synthesis of important molecules such as unnatural α-amino acids and late-stage functionalization of bioactive compounds, and will be useful for modern peptide synthesis and drug discovery.

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“…Besides, the SOMO activation strategy has been extended to the γ-alkylation of enal via a dienamine intermediate formed by condensation with proline-derived catalyst 5 . SET oxidation of the dienamine delivers the corresponding 5–π-electron radical cation 44 , and subsequent enantioselective radical homo- or heterocoupling affords chiral bis-enal in high diastereoselectivity and enantioselectivity (Fig. 4b ).…”

Section: Introductionmentioning

confidence: 99%

Catalytic enantioselective C(sp3)–H functionalization involving radical intermediates

Zhang

et al. 2021

Nat Commun

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Recently, with the boosted development of radical chemistry, enantioselective functionalization of C(sp3)–H bonds via a radical pathway has witnessed a renaissance. In principle, two distinct catalytic modes, distinguished by the steps in which the stereochemistry is determined (the radical formation step or the radical functionalization step), can be devised. This Perspective discusses the state-of-the-art in the area of catalytic enantioselective C(sp3)–H functionalization involving radical intermediates as well as future challenges and opportunities.

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Catalytic Asymmetric Oxidative γ‐Coupling of α,β‐Unsaturated Aldehydes with Air as the Terminal Oxidant

Cited by 36 publications

References 47 publications

Direct Enantio‐ and Diastereoselective Oxidative Homocoupling of Aldehydes

Direct Enantio‐ and Diastereoselective Oxidative Homocoupling of Aldehydes

Visible Light Induced Cu-Catalyzed Asymmetric C(sp³)–H Alkylation

Catalytic enantioselective C(sp3)–H functionalization involving radical intermediates

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Catalytic Asymmetric Oxidative γ‐Coupling of α,β‐Unsaturated Aldehydes with Air as the Terminal Oxidant

Cited by 36 publications

References 47 publications

Direct Enantio‐ and Diastereoselective Oxidative Homocoupling of Aldehydes

Direct Enantio‐ and Diastereoselective Oxidative Homocoupling of Aldehydes

Visible Light Induced Cu-Catalyzed Asymmetric C(sp3)–H Alkylation

Catalytic enantioselective C(sp3)–H functionalization involving radical intermediates

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Product

Resources

About

Visible Light Induced Cu-Catalyzed Asymmetric C(sp³)–H Alkylation