80325-62-8

Upstream product

• 64-19-7 acetic acid 
• 82027-11-0 Methanesulfonic acid (1R,2S,4S)-2-benzoyl-bicyclo[2.2.1]hept-2-yl ester 
• 497-38-1 Norbornan-2-on 
• 98-07-7 Benzotrichlorid 
• 82027-17-6 Phenyl-((1R,2S,4S)-2-trimethylsilanyloxy-bicyclo[2.2.1]hept-2-yl)-methanone 
• 34546-64-0 ((1S,2R,4R)-2-Hydroxy-bicyclo[2.2.1]hept-2-yl)-phenyl-methanone 
• 82027-18-7 Methanesulfinic acid (1S,2R,4R)-2-benzoyl-bicyclo[2.2.1]hept-2-yl ester 
• 82027-17-6 Phenyl-(2-trimethylsilanyloxy-bicyclo[2.2.1]hept-2-yl)-methanone 
• 34546-65-1 ((1R,2R,4S)-2-Hydroxy-bicyclo[2.2.1]hept-2-yl)-phenyl-methanone 
• 95800-13-8 Methanesulfonic acid (1S,2S,4R)-2-benzoyl-bicyclo[2.2.1]hept-2-yl ester 
• 108-24-7 acetic anhydride 
• 2923-18-4 sodium 2,2,2-trifluoroacetate 
• 127-09-3 sodium acetate 
• 75-89-8 2,2,2-trifluoroethanol 

Relevant academic research and scientific papers

Cathodic Addition of Benzylidyne Trichloride to Ketones and Aldehydes

Ketones are converted to homologated enones 7a-g in good yields by cathodic addition of benzylidyne trichloride (1d).As intermediates α-Chlorooxiranes 6 are assumed, which rearrange via α-keto carbenium ions 9 to enones.The intermediacy of 9 is supported by the addition of 1d to norcamphor, where the products indicate equilibrating norbornyl cations as intermediates. α,β-Unsaturated ketones lead depending on steric shielding of the double bond to the cyclopropane 23 as 1,4-adduct or the enone 26 as 1,2-adduct.With aldehydes and 1d, α-chloro or βhydroxy ketones, the conversion products of 2-chlorooxiranes, are obtained.

Diels-Alder Approach to Bicyclic α-Hydroxy Ketones. Facile Ketol Rearrangements of Strained α-Hydroxy Ketones

The trimethylsiloxy-substituted dienophiles 1-benzoyl-1-(trimethylsiloxy)ethylene, 6, 1-carbomethoxy-1-(trimethylsiloxy)ethylene, 12, and 1-acetyl-1-(trimethylsiloxy)ethylene, 4, all reacted with cyclopentadiene to give adducts in which the carbonyl containing substituent of the major product occupied the exo position, in violation of the Alder rule.Desilylation of the Diels-Alder adducts of cyclopentadiene with 4 and 6 led to ring-expanded ketol rearrangement products on silica gel chromatography.This facile rearrangement was attributed to relief of strain in the star ting α-hydroxy ketone.Equilibration studies showed that in the rearranged 2-hydroxy-2-substituted bicyclooctan-3-one systems 24 and 30, the more stable isomer is the one in which the phenyl or methyl substituent is in the axial position.The presence of a strong intramolecular hydrogen bond of the equatorial hydroxyl group with the carbonyl group accounts for the greater stability of 24 and 30.Acetolysis of endo-2-benzoyl-exo-2-norbornyl mesylate, 2, occurred readily, giving mainly the rearranged product of internal return, 1-benzoyl-exo-norbornyl mesylate, 38.The high reactivity of 2 relative to the endo analogue and the α-H analogue was attributed to some transition-state carbonyl conjugation with the incipient α-keto cation center as well as possible neighboring ?-participation and/or steric rate enhancement.