903512-07-2

Upstream product

• 108-24-7 acetic anhydride 
• 115085-23-9 1-(4-methoxyphenyl)hept-2-yn-1-ol 
• 123-11-5 4-methoxy-benzaldehyde 
• 693-02-7 hex-1-yne 

Downstream Products

• 1007605-49-3 1-(dec-1-en-5-yn-4-yl)-4-methoxybenzene 
• 1599479-62-5 1-methoxy-4-(3-(trifluoromethyl)hepta-1,2-dien-1-yl)benzene 
• 82297-66-3 (E)-1-(4-methoxyphenyl)hept-1-en-3-one 

Relevant academic research and scientific papers

Domino gold-catalyzed rearrangement and fluorination of propargyl acetates

A combination of IPrAuNTf2 as catalyst in the presence of Selectfluor has been successfully used for the high yielding synthesis of α-fluoroenones via 1,3-acyloxy rearrangement of propargyl acetates followed by Csp2-F bond formation,

Gold-catalyzed efficient preparation of linear α-haloenones from propargylic acetates

Versatile linear α-iodo- and α-bromoenones are prepared efficiently from readily accessible propargylic acetates using 2 mol % of Au(PPh3)NTf2. This reaction is easy to execute and has broad substrate scope. Good to excellent Z-selectivities are observed in the cases of propargylic acetates derived from aliphatic aldehydes.

Gold-catalyzed efficient preparation of linear α-lodoenones from propargylic acetates

Only 2 mol % of Au(PPh3)NTf2 is needed to convert readily accessible propargylic acetates into versatile linear α-iodoenones in good to excellent yields. This reaction is easy to execute and has broad substrate scope. Good to excellent Z-selectivities are observed in the cases of aliphatic propargylic acetates derived from aldehydes.

[(NHC)AuI]-catalyzed formation of conjugated enones and enals: An experimental and computational study

The [(NHC)AuI]-catalyzed (NHC = N-heterocyclic carbene) formation of α,β-unsaturated carbonyl compounds (enones and enals) from propargylic acetates is described. The reactions occur at 60°C in 8 h in the presence of an equimolar mixture of [(NHC)AuCl] and AgSbF6 and produce conjugated enones and enals in high yields. Optimization studies revealed that the reaction is sensitive to the solvent, the NHC, and, to a lesser extent, to the silver salt employed, leading to the use of [(ItBu)AuCl]/ AgSbF6 in THF as an efficient catalytic system. This transformation proved to have a broad scope, enabling the stereoselective formation of (E)-enones and -enals with great structural diversity. The effect of substitution at the propargylic and acetylenic positions has been investigated, as well as the effect of aryl substitution on the formation of cinnamyl ketones. The presence or absence of water in the reaction mixture was found to be crucial. From the same phenylpropargyl acetates, anhydrous conditions led to the formation of indene compounds via a tandem [3,3] sigmatropic rearrangement/intramolecular hydroarylation process, whereas simply adding water to the reaction mixture produced enone derivatives cleanly. Several mechanistic hypotheses, including the hydrolysis of an allenol ester intermediate and SN2′ addition of water, were examined to gain an insight into this transformation. Mechanistic investigations and computational studies support [(NHC)AuOH], produced in situ from [(NHC)AuSbF6] and H 2O, instead of cationic [(NHC)AuSbF6] as the catalytically active species. Based on DFT calculations performed at the B3LYP level of theory, a full catalytic cycle featuring an unprecedented transfer of the OH moiety bound to the gold center to the C≡C bond leading to the formation of a gold-allenolate is proposed.

AuI-catalyzed tandem [3,3] rearrangement-intramolecular hydroarylation: Mild and efficient formation of substituted indenes

(Chemical Equation Presented) Dignified auration: The rearrangement of phenylpropargyl acetates to substituted indenes is catalyzed by [Au 1(NHC)] complexes (see scheme, NHC = N-heterocyclic carbene) under extremely mild reaction conditions. This chemoselective transformation involves 1,3-migration of the acetate group and is proposed to proceed through an allene intermediate. TMS = trimethylsilyl, TBS = tert-butyldimethylsilyl.