Asymmetric Synthesis of Dihydropyranones via Gold(I)‐Catalyzed Intermolecular [4+2] Annulation of Propiolates and Alkenes

Kim, Hanbyul; Choi, Su Yeon; Shin, Seunghoon

doi:10.1002/anie.201807514

Cited by 28 publications

(16 citation statements)

References 75 publications

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“…In 2018, Shin and co‐workers [10] reported another intramolecular example of annulation between alkynes and alkenes. Adopting ( R )‐DM‐Segphos(AuCl) 2 as the catalyst, they demonstrated intermolecular [4+2] annulation of propiolates and alkenes affording dihydropyranones as the major product (Scheme 5).…”

Section: Recent Development Of Enantioselective Gold(i) Catalysismentioning

confidence: 99%

Recent Advances in the Development of Chiral Gold Complexes for Catalytic Asymmetric Catalysis

Jiang

Wong

2021

Chemistry An Asian Journal

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Asymmetric gold catalysis has been rapidly developed in the past ten years. Breakthroughs have been made by rational design and meticulous selection of chiral ligands. This review summarizes newly developed gold‐catalyzed enantioselective organic transformations and recent progress in ligand design (since 2016), organized according to different types of chiral ligands, including bisphosphine ligands, monophosphine ligands, phosphite‐derived ligands, and N‐heterocyclic carbene ligands for asymmetric gold(I) catalysis as well as heterocyclic carbene ligands and oxazoline ligands for asymmetric gold(III) catalysis.

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Section: Recent Development Of Enantioselective Gold(i) Catalysismentioning

confidence: 99%

Recent Advances in the Development of Chiral Gold Complexes for Catalytic Asymmetric Catalysis

Jiang

Wong

2021

Chemistry An Asian Journal

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“…Initially, when ligand ( R )‐ L22b was used α,β‐unsaturated δ‐lactones were obtained with a maximum of 65 % ee. Later, under slightly different conditions and using sodium dodecyl sulphate (SDS) as an anionic surfactant, lactones 59 were obtained with better enantioselectivities [57] …”

Section: Intermolecular Gold(i) Catalyzed Reactions Of Alkynesmentioning

confidence: 99%

“…Later, under slightly different conditions and using sodium dodecyl sulphate (SDS) as an anionic surfactant, lactones 59 were obtained with better enantioselectivities. [57] …”

Section: Intermolecular Gold(i) Catalyzed Reactions Of Alkynesmentioning

confidence: 99%

New‐Generation Ligand Design for the Gold‐Catalyzed Asymmetric Activation of Alkynes

et al. 2021

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Gold(I) catalysts are ideal for the activation of alkynes under very mild conditions. However, unlike allenes or alkenes, the triple bond of alkynes cannot be prochiral. In addition, the linear coordination displayed by gold(I) complexes places the chiral ligand far away from the substrate resulting in an inefficient transfer of chiral information. This poses a significant challenge for the achievement of high enantiocontrol in gold(I)‐catalyzed reactions of alkynes. Although considerable progress on enantioselective gold(I)‐catalyzed transformations has recently been achieved, the asymmetric activation of non‐prochiral alkyne‐containing small molecules still represents a great challenge. Herein we summarize recent advances in intra‐ and intermolecular enantioselective gold(I)‐catalyzed reactions involving alkynes, discussing new chiral ligand designs that lie at the basis of these developments. We also focus on the mode of action of these catalysts, their possible limitations towards a next‐generation of more efficient ligand designs. Finally, square planar chiral gold(III) complexes, which offer an alternative to chiral gold(I) complexes, are also discussed.

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“…As fundamental structural scaffolds, cyclopentenones [18][19][20][21][22][23] and dihydropyranones [24][25][26][27][28][29] widely exist in numerous natural products, biologically active compounds, and drugs, such as the antibiotics pentenomycins 18 and antitumor active (+)-altholactone 24 (Fig. 1c).…”

Section: Introductionmentioning

confidence: 99%

Solvent-controlled photocatalytic divergent cyclization of alkynyl aldehydes: access to cyclopentenones and dihydropyranols

Zhu

Zheng

Zhang

et al. 2021

Preprint

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Divergent synthesis is a powerful strategy for the fast assembly of different molecular scaffolds from the identical starting materials. We describe here a novel solvent-controlled photocatalytic divergent cyclization of alkynyl aldehydes with sulfonyl chlorides for the direct construction of highly functionalized cyclopentenones and dihydropyranols that widely exist in bioactive molecules and natural products. Density functional theory calculations suggest that an unprecedented N,N-dimethylacetamide-assisted 1,2-hydrogen transfer of alkoxy radicals is responsible for the cyclopentenone formation, whereas a C-C cleavage accounts for the selective production of dihydropyranols in acetonitrile. Given the simple and mild reaction conditions, excellent functional group compatibility, forming up to four chemical bonds, and tunable selectivity, it may find wide applications in synthetic chemistry.

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Asymmetric Synthesis of Dihydropyranones via Gold(I)‐Catalyzed Intermolecular [4+2] Annulation of Propiolates and Alkenes

Cited by 28 publications

References 75 publications

Recent Advances in the Development of Chiral Gold Complexes for Catalytic Asymmetric Catalysis

Recent Advances in the Development of Chiral Gold Complexes for Catalytic Asymmetric Catalysis

New‐Generation Ligand Design for the Gold‐Catalyzed Asymmetric Activation of Alkynes

Solvent-controlled photocatalytic divergent cyclization of alkynyl aldehydes: access to cyclopentenones and dihydropyranols

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