134240-74-7

Upstream product

• 1817-51-2 1-phenyl-1-hexyn-3-ol 
• 108-24-7 acetic anhydride 
• 64846-61-3 phenylacetylenic zinc bromide 
• 134240-70-3 Acetic acid 1-benzotriazol-1-yl-butyl ester 
• 536-74-3 phenylacetylene 
• 29949-17-5 1,1-diacetoxybutane 
• 14252-32-5 1-phenyl-hex-1-yn-3-one 
• 123-72-8 butyraldehyde 

Downstream Products

• 1263314-69-7 (E)-2-fluoro-1-phenylhex-2-en-1-one 
• 1263314-70-0 (Z)-2-fluoro-1-phenylhex-2-en-1-one 
• 130786-21-9 (E)-1,2-diphenylhex-2-en-1-one 
• 42925-43-9 (E)-1-phenylhex-2-en-1-one 
• 56438-82-5 (Z)-1-phenyl-hex-2-en-1-one 

Relevant academic research and scientific papers

Intramolecular and Ferrier Rearrangement Strategy for the Construction of C1-β-d-xylopyranosides: Synthesis, Mechanism and Biological Activity Study

A stereoselective synthesis of C1-β-d-xylopyranoside derivatives had been developed via intramolecular 1,3-acyloxy migration/Ferrier rearrangement stategy from readily available propargylic carboxylates and d-xylal. A combined catalytic system of chloro(t

Gold-catalyzed diastereoselective synthesis of α-fluoroenones from propargyl acetates

A diastereoselective preparation of -fluoroenones from propargyl acetates has been developed proceeding via a gold-catalyzed rearrangement-fluorination cascade. Control reactions are consistent with a mechanism involving a gold-mediated 3,3-sigmatropic shift followed by a direct, nongold-catalyzed electrophilic fluorination of the allenyl acetate intermediate.

[(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.

TiCl4-mediated nucleophilic substitution of propargylic esters

Direct displacement reactions of propargylic esters are reported. 10 mol% of TiCl4 were used to carry out a nucleophilic substitution. Scope and limitation of this novel reaction are described. (C) 2000 Elsevier Science Ltd.

Benzotriazole: A novel synthetic auxiliary

Benzotriazole and aldehydes react reversibly to give addition products: in the presence of amines and other NH-compounds water can be eliminated to form products of type Bt-CHR-NR′R″. The latter are versatile intermediates for the preparation of primary, secondary, and tertiary amines and in the alkylation of hydroxylamines, hydrazines, amides, thioamides, and sulfonamides. Polyfunctional amines and other polyfunctional compounds can also be prepared, and they enable significant extending of Mannich reaction. Similar oxygen compounds Bt-CRR′-OR″ enable new syntheses of ethers and esters. Reactions in which benzotriazole is eliminated rather than substituted open up new pathways to enamines, enol ethers, and nitrones. The methodology is capable of extension to a variety of vinylogous systems including benzenoid and heteroaromatic derivatives. In addition to acting as a versatile leaving group, benzotriazolyl residues activate neighboring CH bonds to proton loss and a variety of such applications is described.

A novel synthesis of esters via substitution of the benzotriazolyl group in 1-(benzotriazol-1-yl)alkyl esters with organozinc reagents

Aldehydes are converted by thionyl chloride and benzotriazole into 1-(1-chloroalyl)benzotriazoles which react with sodium carboxylates to give 1-(benzotriazol-1-yl)alkyl esters. 3. In the alternative route, 3 are prepared by substitution of one of the acetoxy groups in acylals with benzotriazole. The benzotriazolyl moiety in 3 is substituted by an alkyl, an aryl or an alkynyl group upon treatment with an organic reagent in a new versatile synthesis of esters 4.