Catalyst‐Dependent Stereospecific [3,3]‐Sigmatropic Rearrangement of Sulfoxide‐Ynamides: Divergent Synthesis of Chiral Medium‐Sized <i>N</i>,<i>S</i>‐Heterocycles

Zhu, Guangyu; Zhou, Ji-Jia; Liu, Li-Gao; Xiao, Li; Zhu, Xin‐Qi; Lü, Xin; Zhou, Jin‐Mei; Ye, Long‐Wu

doi:10.1002/ange.202204603

Cited by 9 publications

(1 citation statement)

References 79 publications

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“…In 2018, our group disclosed a strategy for the synthesis of α,β-disubstituted 1,4-dicarbonyl compounds, allowing highly stereoselective access to all four possible isomers (Figure A, top ). , Mechanistically, we proposed initiation by forming keteniminium ion III through protonation of the ynamide reactant, followed by the addition of vinyl sulfoxide I . This would generate an adduct ( IV ) that undergoes a key charge-accelerated [3,3]-sigmatropic sulfonium rearrangement, ultimately yielding the corresponding aldothionium ion intermediate V in a stereoselective fashion. − This resulting species is hydrolyzed in situ to afford a 1,4-dicarbonyl compound.…”

Section: Introductionmentioning

confidence: 99%

Stereodivergent Synthesis of 1,4-Dicarbonyl Compounds through Sulfonium Rearrangement: Mechanistic Investigation, Stereocontrolled Access to γ-Lactones and γ-Lactams, and Total Synthesis of Paraconic Acids

G.-Simonian,

Spieß,

Riomet

et al. 2024

J. Am. Chem. Soc.

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Although simple γ-lactones and γ-lactams have received considerable attention from the synthetic community, particularly due to their relevance in biological and medicinal contexts, stereoselective synthetic approaches to more densely substituted derivatives remain scarce. The in-depth study presented herein, showcasing a straightforward method for the stereocontrolled synthesis of γ-lactones and γ-lactams, builds on and considerably expands the stereodivergent synthesis of 1,4-dicarbonyl compounds by a ynamide/vinyl sulfoxide coupling. A full mechanistic and computational study of the rearrangement was conducted, uncovering the role of all of the reaction components and providing a rationale for stereoselection. The broad applicability of the developed tools to streamlining synthesis is demonstrated by concise enantioselective total syntheses of (+)-nephrosteranic acid, (+)-rocellaric acid, and (+)-nephromopsinic acid.

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Section: Introductionmentioning

confidence: 99%

Stereodivergent Synthesis of 1,4-Dicarbonyl Compounds through Sulfonium Rearrangement: Mechanistic Investigation, Stereocontrolled Access to γ-Lactones and γ-Lactams, and Total Synthesis of Paraconic Acids

G.-Simonian,

Spieß,

Riomet

et al. 2024

J. Am. Chem. Soc.

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Enantioselective Copper‐Catalyzed Formal [2+1] and [4+1] Annulations of Diynes with Ketones via Carbonyl Ylides

Huang

et al. 2022

Angewandte Chemie

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Carbonyl ylides have proven to be powerful synthons for the efficient construction of various valuable O‐heterocycles, and the formation of carbonyl ylides by the reaction of metal carbenes with carbonyls has attracted increasing attention over the past decades. However, a catalyst‐controlled highly enantioselective reaction of carbonyl ylides from metal carbenes is extremely challenging. Herein, we report a novel copper‐catalyzed asymmetric formal [2+1] and [4+1] annulations of diynes with ketones via carbonyl ylides. Importantly, this protocol not only represents the first example of successful asymmetric epoxidation via carbonyl ylides, but also constitutes the first reaction of vinyl cations with carbonyl compounds. This method leads to the divergent, practical and atom‐economical synthesis of a range of chiral oxiranes and dihydrofurans in moderate to excellent yields with generally excellent enantioselectivities and diastereoselectivities via remote‐stereocontrol strategy.

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I₂‐Catalyzed Cycloisomerization of Ynamides: Chemoselective and Divergent Access to Indole Derivatives

Zhu

Nie

et al. 2023

Angewandte Chemie

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Herein, an I 2 -catalyzed unprecedented cycloisomerization of ynamides is developed, furnishing various functionalized bis(indole) derivatives in generally good to excellent yields with wide substrate scope and excellent atom-economy. This protocol not only represents the first molecular-iodine-catalyzed tandem complex alkyne cycloisomerizations, but also constitutes the first chemoselective cycloisomerization of tryptamine-ynamides involving distinctively different C-(sp 3 )À C(sp 3 ) bond cleavage and rearrangement. Moreover, chiral tetrahydropyridine frameworks containing two stereocenters are obtained with moderate to excellent diastereoselectivities and excellent enantioselectivities. Meanwhile, cycloisomerization and aromatization of ynamides produce pyrrolyl indoles with high efficiency enabled by I 2 . Additionally, control experiments and theoretical calculations reveal that this reaction probably undergoes a tandem 5-exo-dig cyclization/rearrangement process.

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Catalyst‐Dependent Stereospecific [3,3]‐Sigmatropic Rearrangement of Sulfoxide‐Ynamides: Divergent Synthesis of Chiral Medium‐Sized N,S‐Heterocycles

Cited by 9 publications

References 79 publications

Stereodivergent Synthesis of 1,4-Dicarbonyl Compounds through Sulfonium Rearrangement: Mechanistic Investigation, Stereocontrolled Access to γ-Lactones and γ-Lactams, and Total Synthesis of Paraconic Acids

Stereodivergent Synthesis of 1,4-Dicarbonyl Compounds through Sulfonium Rearrangement: Mechanistic Investigation, Stereocontrolled Access to γ-Lactones and γ-Lactams, and Total Synthesis of Paraconic Acids

Enantioselective Copper‐Catalyzed Formal [2+1] and [4+1] Annulations of Diynes with Ketones via Carbonyl Ylides

I₂‐Catalyzed Cycloisomerization of Ynamides: Chemoselective and Divergent Access to Indole Derivatives

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Catalyst‐Dependent Stereospecific [3,3]‐Sigmatropic Rearrangement of Sulfoxide‐Ynamides: Divergent Synthesis of Chiral Medium‐Sized N,S‐Heterocycles

Cited by 9 publications

References 79 publications

Stereodivergent Synthesis of 1,4-Dicarbonyl Compounds through Sulfonium Rearrangement: Mechanistic Investigation, Stereocontrolled Access to γ-Lactones and γ-Lactams, and Total Synthesis of Paraconic Acids

Stereodivergent Synthesis of 1,4-Dicarbonyl Compounds through Sulfonium Rearrangement: Mechanistic Investigation, Stereocontrolled Access to γ-Lactones and γ-Lactams, and Total Synthesis of Paraconic Acids

Enantioselective Copper‐Catalyzed Formal [2+1] and [4+1] Annulations of Diynes with Ketones via Carbonyl Ylides

I2‐Catalyzed Cycloisomerization of Ynamides: Chemoselective and Divergent Access to Indole Derivatives

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I₂‐Catalyzed Cycloisomerization of Ynamides: Chemoselective and Divergent Access to Indole Derivatives