Ambivalent Reactivity Modes of β‐Chlorovinyl Ketones: Electrophilic Lithium [3]Cumulenolates from Soft Vinyl Enolization Strategy

Kim, Hun Young; Rooney, Edward Oscar; Meury, Raymond Phillip; Oh, Kyungsoo

doi:10.1002/ange.201302750

Cited by 9 publications

(3 citation statements)

References 42 publications

(38 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Alternatively, the presence of aldehydes 25 builds aldol derivatives 23 c (Scheme 6d) [38] . Also, self‐condensation products 23 d are obtained when the reaction is performed in the presence of lithium salts (Scheme 6e) [39] …”

Section: Synthesis Of Allenonesmentioning

confidence: 99%

See 1 more Smart Citation

Highlighting the Rich Chemistry of the Allenone Moiety

Almendros

Alonso

2023

Adv Synth Catal

View full text Add to dashboard Cite

Conjugated and non-conjugated allenones appear as recurring motifs in organic synthesis, natural products and mechanistic investigations showing unique properties and applications. The ability of allenones to build cycles has provided a direct access to strained systems, medium-sized rings, arenes, heterocycles and complex polycycles. In addition, allenones have served as models in mechanistic investigations and catalysis. The critic compilation herein presented will provide an exhaustive overview of the synthetic possibilities allenones may offer, which certainly will inspire our community in their search of more efficient synthetic methodologies, preparation of biological and pharmaceutical targets, and improve our knowledge in theoretical organic chemistry. Great part of this review will discuss synthetic aspects, catalysis innovation and mechanistic insights of the chemical transformations implying the allenone motif. In addition, many examples on total synthesis and pharmacologically active compounds will be described. We hope that this overview will be attractive to the organic chemistry, synthetic chemistry, catalysis, theoretical chemistry, natural products and medicinal chemistry communities. 3.5. Synthesis of Spirocycles and Bridged Structures 3.6. Open-Chain Structures from Allenones 3.7. Allenones in Total Synthesis 4.

show abstract

Section: Synthesis Of Allenonesmentioning

confidence: 99%

“…[38] Also, self-condensation products 23 d are obtained when the reaction is performed in the presence of lithium salts (Scheme 6e). [39]…”

Section: Generation Of Allenes In Carbonyl Compoundsmentioning

confidence: 99%

Highlighting the Rich Chemistry of the Allenone Moiety

Almendros

Alonso

2023

Adv Synth Catal

View full text Add to dashboard Cite

show abstract

“…2 This reaction pathway has paved a way to generate versatile synthetic intermediate species with on demand reactivity, nucleophilic or electrophilic, where the characteristics of reacting partners could be modulated. 3 The planar conformation of (Z)-βchlorovinyl ketones displays an α-vinyl enolization significantly slower than that of (E)-β-chlorovinyl ketones, and the reaction under increased temperature competitively produces the quaternary salts through the Michael addition of Et 3 N to (Z)-β-chlorovinyl ketones. 2 Thus, at the present time, the synthetic utility of (Z)-β-chlorovinyl ketones via the α-vinyl enolization strategy remains largely unexplored.…”

mentioning

confidence: 99%

Tandem Transformations via Friedel–Crafts Acylation Followed by a Ring-Expansion, Ring-Opening, and Cycloisomerization Sequence

Kim

2019

Org. Lett.

Self Cite

View full text Add to dashboard Cite

A tandem synthetic route to a diverse array of cyclic compounds has been developed from Friedel–Crafts acylation of alkynes followed by the microwave irradiation of β-chlorovinyl ketone intermediates. The stereoisomeric β-chlorovinyl ketone intermediates smoothly underwent a thermal α-vinyl enolization and ring expansion to vinyl and carbocyclic furans as well as cyclopetene derivatives in good to excellent yields without the need for any catalysts.

show abstract

Cu(OTf)₂‐Catalyzed Aerobic Cycloisomerization of Alkenyl Sulfones to Furans Using (E)‐β‐Chlorovinyl Ketones and Sodium Sulfinates

Bhatt

Kim

2022

Adv Synth Catal

Self Cite

View full text Add to dashboard Cite

Sodium sulfinate addition to (E)-β-chlorovinyl ketones followed by the aerobic cycloisomerization of alkenyl sulfone intermediates has been established for the synthesis of 3-sulfonyl furans. The optimal cycloisomerization catalyst system was identified to be Cu(OTf) 2 , where molecular oxygen acts as a terminal oxidant. With three points of structural variation in both β-chlorovinyl ketones and sodium sulfinates, the current aerobic cycloisomerization strategy allows the synthesis of highly functionalized and substituted furan derivatives.

show abstract

Ambivalent Reactivity Modes of β‐Chlorovinyl Ketones: Electrophilic Lithium [3]Cumulenolates from Soft Vinyl Enolization Strategy

Abstract: Scheme 1. Known and proposed reactivity patterns of functionalized allenes and [3]cumulenes. Scheme 2. Ambivalent reactivity modes of in situ generated oxy-substituted [3]cumulenes.

Cited by 9 publications

References 42 publications

Highlighting the Rich Chemistry of the Allenone Moiety

Highlighting the Rich Chemistry of the Allenone Moiety

Tandem Transformations via Friedel–Crafts Acylation Followed by a Ring-Expansion, Ring-Opening, and Cycloisomerization Sequence

Cu(OTf)₂‐Catalyzed Aerobic Cycloisomerization of Alkenyl Sulfones to Furans Using (E)‐β‐Chlorovinyl Ketones and Sodium Sulfinates

Contact Info

Product

Resources

About

Ambivalent Reactivity Modes of β‐Chlorovinyl Ketones: Electrophilic Lithium [3]Cumulenolates from Soft Vinyl Enolization Strategy

Abstract: Scheme 1. Known and proposed reactivity patterns of functionalized allenes and [3]cumulenes. Scheme 2. Ambivalent reactivity modes of in situ generated oxy-substituted [3]cumulenes.

Cited by 9 publications

References 42 publications

Highlighting the Rich Chemistry of the Allenone Moiety

Highlighting the Rich Chemistry of the Allenone Moiety

Tandem Transformations via Friedel–Crafts Acylation Followed by a Ring-Expansion, Ring-Opening, and Cycloisomerization Sequence

Cu(OTf)2‐Catalyzed Aerobic Cycloisomerization of Alkenyl Sulfones to Furans Using (E)‐β‐Chlorovinyl Ketones and Sodium Sulfinates

Contact Info

Product

Resources

About

Cu(OTf)₂‐Catalyzed Aerobic Cycloisomerization of Alkenyl Sulfones to Furans Using (E)‐β‐Chlorovinyl Ketones and Sodium Sulfinates