892875-11-5

Upstream product

• 150765-78-9 2-methyl-3-oxocyclohex-1-en-1-yl trifluoromethanesulfonate 
• 1193-55-1 2-methylcyclohexane-1,3-dione 

Downstream Products

• 197292-38-9 3-(tert-butyldimethylsiloxy)-2-methylcyclohex-1-enyl trifluoromethanesulfonate 
• 146801-29-8 5,5,5-trifluoro-4-hydroxy-4-phenylpentan-2-one 
• 197292-39-0 (E)-4-[3'-(tert-butyldimethylsiloxy)-2'-methylcyclohex-1'-enyl]but-3-en-2-one 
• 58944-42-6 hept-5-yn-1-ol 

Relevant academic research and scientific papers

Copper-Catalyzed Enantioselective 1,2-Reduction of Cycloalkenones

We report an asymmetric 1,2-reduction of cyclic α,β-unsaturated ketones to access various enantiomerically enriched cyclic allylic alcohols under mild conditions, catalyzed by in situ generated copper hydride ligated with (R)-DTBM-C3*-TunePhos. α-Brominated cycloalkenones were reduced with excellent enantioselectivities of up to 98% ee, while substrates that were without α-substituents were reduced chemoselectively, with moderate enantioselectivities.

A Catalytic Strategy for α,ω-Functionalization: NHC-Mediated Fragmentation/Umpolung Cascades to Access Hydroxytrifluoromethyl Ynones and Allenones

Herein we report an unprecedented, convenient NHC-catalyzed one-pot cascade reaction to afford α,ω-difunctionalized hydroxytrifluoromethyl alkynones and allenones in a single step. The critical fragile aliphatic aldehydes are introduced by a base-mediated in situ Grob-type fragmentation of their corresponding latent cyclic vinylogous hemiacetal triflate (VHAT) and γ-hydroxy vinyl triflate (GHVT) precursors, avoiding typical problems and losses upon isolation. The ′demasked′ aldehydes are subsequently trapped by NHC-catalyzed umpolung and further metal-free C?C-cross-coupling to access a broad scope of terminally modified alkynyl or allenyl aliphatic, aromatic and heteroaromatic trifluoromethyl ketones as multifunctionalized, high-value building blocks for advanced synthetic applications. Additional synthetic utility of this approach is demonstrated with the possibility for asymmetric variants using chiral NHC-catalysts.

Reaction Discovery Using Neopentylene-Tethered Coupling Partners: Cycloisomerization/Oxidation of Electron-Deficient Dienynes

A rhodium-catalyzed cycloisomerization and oxidation of tethered dienynes for the synthesis of indanes is described. An auxiliary fragmentation/olefination method (also described herein) provides novel access to tethered alkyne-dienoate substrates. The re

Synthesis of high-value 1,6-enynes by tandem fragmentation/olefination

A tandem process provides high-value 1,6-enynes that are otherwise difficult to prepare. Two base-mediated reactions - fragmentation and olefination - are executed in a coordinated manner that is overall more efficient than either reaction on its own. The

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.

Cyclic vinylogous triflate hemiacetals as new surrogates for alkynyl aldehydes

Cyclic vinylogous triflate hemiacetals can serve as 'synthetic equivalents' for alkynyl aldehydes: treatment of a vinylogous triflate hemiacetal with excess amounts of Grignard reagents produces acyclic alkynyl alcohols in good to high yields. This transf

Carotenoids and related polyenes. Part 4. Synthesis of carotenoid analogues containing a conjugated carbonyl group and their fluorescence properties

Fluorescence properties of several synthetic carotenoid analogues have been investigated in order to assess the relationship between molecular structures and function as a photosynthetic antenna. The origin of fluorescence is determined by two factors; th