Carbene‐Catalyzed Dynamic Kinetic Resolution and Asymmetric Acylation of Hydroxyphthalides and Related Natural Products

Liu, Yingguo; Majhi, Pankaj Kumar; Song, Runjiang; Mou, Chengli; Hao, Lin; Chai, Huifang; Jin, Zhichao; Robin, Yonggui

doi:10.1002/anie.201912926

Cited by 31 publications

(16 citation statements)

References 43 publications

(19 reference statements)

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“…In addition, methyl 2-formylbenzoate ( 10 ) could also work well under the optimal conditions, affording the desired product 3a in good yield (Scheme 5 , eq 2). On the basis of these experimental results and previous reports, 3e f 12 two plausible reaction mechanisms for the formation of 3-difluoroalkylated phthalides with phthalaldehydic acids and difluoroenoxysilanes are proposed in Scheme 5 . In path a, the phthalaldehydic acid substrate I undergoes an equilibrium with the corresponding hydrophthalide (the major form in most solvents).…”

Section: Table 1 Optimization Of the Conditions For The Reaction Of Phthalaldehydic Acid With Difluoroenoxysilane supporting

confidence: 64%

p-Toluenesulfonic Acid-Catalyzed Reaction of Phthalaldehydic Acids with Difluoroenoxysilanes: Access to 3-Difluoroalkyl Phthalides

Liu

Wang

et al. 2021

Synthesis

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A convenient approach for the synthesis of 3-difluoroalkyl phthalides has been developed from phthalaldehydic acids and difluoroenoxysilanes by using relatively inexpensive p-toluenesulfonic acid monohydrate (PTSA) as a catalyst. A series of 3-difluoroalkyl phthalides and cyclic difluoroalkyl ethers were obtained in up to 99% yield. The products obtained could be readily converted into difluoroalkyl phthalide derivatives by simple modifications.

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Section: Table 1 Optimization Of the Conditions For The Reaction Of Phthalaldehydic Acid With Difluoroenoxysilane supporting

confidence: 64%

p-Toluenesulfonic Acid-Catalyzed Reaction of Phthalaldehydic Acids with Difluoroenoxysilanes: Access to 3-Difluoroalkyl Phthalides

Liu

Wang

et al. 2021

Synthesis

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“…For oxidative functionalization of aldehyde carbonyl carbon, an NHC-catalyzed dynamic kinetic resolution of hemiacetal was selected as a model reaction 64 , 65 and the results were shown in Fig. 5 (see Supplementary Information for details of condition optimization).…”

Section: Resultsmentioning

confidence: 99%

Electroredox carbene organocatalysis with iodide as promoter

Zhou

Lan

et al. 2022

Nat Commun

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Oxidative carbene organocatalysis, inspired from Vitamin B1 catalyzed oxidative activation from pyruvate to acetyl coenzyme A, have been developed as a versatile synthetic method. To date, the α-, β-, γ-, δ- and carbonyl carbons of (unsaturated)aldehydes have been successfully activated via oxidative N-heterocyclic carbene (NHC) organocatalysis. In comparison with chemical redox or photoredox methods, electroredox methods, although widely used in mechanistic study, were much less developed in NHC catalyzed organic synthesis. Herein, an iodide promoted electroredox NHC organocatalysis system was developed. This system provided general solutions for electrochemical single-electron-transfer (SET) oxidation of Breslow intermediate towards versatile transformations. Radical clock experiment and cyclic voltammetry results suggested an anodic radical coupling pathway.

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“…For oxidative functionalization of aldehyde carbonyl carbon, an NHC-catalyzed dynamic kinetic resolution of hemiacetal was selected as a model reaction 61 and the results were shown in Fig. 5 (see Supplementary Information for details of condition optimization).…”

Section: Resultsmentioning

confidence: 99%

Electroredox Carbene Organocatalysis with iodine cocatalyst

Zhou¹,

Li²,

Lan³

et al. 2022

Preprint

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Oxidative carbene organocatalysis, inspired from Vitamin B1 catalyzed oxidative activation from pyruvate to acetyl coenzyme A, have been developed as a versatile synthetic method. To date, the α-, β-, γ-, δ- and carbonyl carbons of (unsaturated)aldehydes have been successfully activated via oxidative N-heterocyclic carbene (NHC) organocatalysis. In comparison with chemical redox or photoredox methods, electroredox methods, although widely used in mechanistic study, were much less studied in NHC catalyzed organic synthesis. Herein, an electroredox NHC organocatalysis system with iodine cocatalyst was developed. With the help of non-uniform distribution of electrolysis system, NHC and iodine, which was normally not compatible in chemical reaction, cooperated well in the electrochemical system. This cocatalyst system provided general solutions for electrochemical single-electron-transfer (SET) oxidation of Breslow intermediate towards versatile transformations. Radical clock experiment and cyclic voltammetry results suggested an anodic radical coupling pathway.

show abstract

Carbene‐Catalyzed Dynamic Kinetic Resolution and Asymmetric Acylation of Hydroxyphthalides and Related Natural Products

Cited by 31 publications

References 43 publications

p-Toluenesulfonic Acid-Catalyzed Reaction of Phthalaldehydic Acids with Difluoroenoxysilanes: Access to 3-Difluoroalkyl Phthalides

p-Toluenesulfonic Acid-Catalyzed Reaction of Phthalaldehydic Acids with Difluoroenoxysilanes: Access to 3-Difluoroalkyl Phthalides

Electroredox carbene organocatalysis with iodide as promoter

Electroredox Carbene Organocatalysis with iodine cocatalyst

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