125488-50-8

Upstream product

• 126-81-8 dimedone 
• 10416-78-1 5,5-dimethyl-3-((trimethylsilyl)oxy)cyclohex-2-en-1-one 
• 1396274-89-7 C₁₂H₁₁F₉O₄S 
• 591-51-5 phenyllithium 
• 76881-19-1 5,5-dimethyl-3-trifluoromethylsulfonyloxycyclohex-2-en-1-one 

Downstream Products

• 1357173-60-4 C₁₆H₂₀O₂ 
• 1357173-11-5 (S)-phenyl(2,5,5-trimethylcyclopent-2-enyl)methanone 
• 1357173-61-5 C₁₇H₂₂O₂ 
• 1357173-06-8 (Z)-(3,3-dimethyl-1-phenylhept-1-en-5-ynyloxy)triethylsilane 
• 1357173-62-6 3,3-dimethyl-1-phenylhept-5-yn-1-one 

Relevant academic research and scientific papers

A tandem carbanion addition/carbon-carbon bond cleavage yields alkynyl ketones

Carbanion addition to vinylogous acid triflates triggers carbon-carbon bond cleavage to form alkynyl ketones under mild conditions. Mechanistic factors affecting the cleavage event and its relationship to complementary fragmentations are discussed. A rang

Tandem nucleophilic addition/fragmentation of vinylogous acyl nonaflates for the synthesis of functionalized alkynes, with new mechanistic insight

Vinylogous acyl nonaflates, like the corresponding triflates, are subject to nucleophile-triggered fragmentation as part of a tandem process for generating functionalized alkynes. Advantages to the use of nonaflates in lieu of triflates include cost and s

Tandem nucleophilic addition/fragmentation reactions and synthetic versatility of vinylogous acyl triflates

A thorough analysis of the chemistry of vinylogous acyl triflates provides insight into important chemical processes and opens new directions in synthetic technology. Tandem nucleophilic addition/C-C bond cleaving fragmentation reactions of cyclic vinylogous acyl triflates 1 yield a variety of acyclic acetylenic compounds. Full details are disclosed herein. A wide array of nucleophiles, such as organolithium and Grignard reagents, lithium enolates and their analogues, hydride reagents, and lithium amides, are applied. The respective reactions produce ketones 2, 1,3-diketones and their analogues 3, alcohols 4, and amides 5. The present reactions are proposed to proceed through a 1,2-addition of the nucleophile to the carbonyl group of starting triflates 1 to form tetrahedral alkoxide intermediates C, followed by Grob-type fragmentation, which effects C-C bond cleavage to yield acyclic acetylenic compounds 2-5 and 7. The potent nucleofugacity of the triflate moiety is channeled through the σ-bond framework of 1, providing direct access to the fragmentation pathway without denying other typical reactions of cyclic vinylogous esters. The synthetic versatility of vinylogous acyl triflates, including functionalization reactions of the cyclic enone core (1 → 6 or 8), is also illustrated.