35234-67-4

Upstream product

• 87518-20-5 2-phenyl-3-trimethylsiloxybicyclo<2.2.1>heptan-2-ene 
• 7485-53-2 endo-3-phenylbicyclo<2.2.1>heptan-2-one 
• 497-38-1 Norbornan-2-on 
• 87518-22-7 (1R,3S,4S)-3-Phenyl-3-trimethylsilanyloxy-bicyclo[2.2.1]heptan-2-one 

Downstream Products

• 71341-11-2 Acetic acid (1S,2S,4R)-3-oxo-2-phenyl-bicyclo[2.2.1]hept-2-yl ester 
• 71341-37-2 Trifluoro-acetic acid (1R,2S,4S)-3-oxo-2-phenyl-bicyclo[2.2.1]hept-2-yl ester 
• 71341-37-2 exo-2-trifluoroacetoxy-endo-2-phenylbicyclo<2.2.1>heptan-3-one 

Relevant academic research and scientific papers

Carbocation-forming reactions in dimethyl sulfoxide

Mesylate derivatives of 3-aryl-3-hydroxy-β-lactams and thiolactams react in DMSO-d6 by first-order processes to give alcohol products. Substituent effect studies implicate carbocation intermediates (ion-pairs) that are captured by DMSO-d6 to give transient oxosulfonium ions. Rapid reaction of the oxosulfonium ions with trace amounts of water leads to the alcohol product and regenerates DMSO-d6. H217O labeling studies show that 17O is incorporated into the DMSO. The mesylate derivatives of endo- and exo-2-hydroxy-2-phenylbicyclo[2.2.1]heptan-3-one also react in DMSO-d6 to give the alcohol products. Ion-pair intermediates that capture DMSO giving unstable oxosulfonium ions are again proposed. Exo-2-phenyl-endo-bicyclo[2.2.1]heptyl trifluoroacetate readily eliminates trifluoroacetic acid in DMSO-d6 via a cationic mechanism involving loss of the endotrifluoroacetate leaving group as well as an exo-hydrogen. The O-methyl oxime derivative of α-chloroα,α-diphenylacetophenone reacts in DMSO-d6 to give 1-methoxy-2,3-diphenylindole, a product derived from cyclization of a cationic intermediate. A common ion rate suppression provides further evidence for a cationic mechanism. The triflate derivative of pivaloin reacts by a cationic mechanism in DMSO-d6 to give rearranged products. The rate is even faster than in highly ionizing solvents such as trifluoroethanol or trifluoroacetic acid. 1-Adamantyl mesylate reacts in DMSO-d6 by a first-order process (YOMs = -4.00) to give a long-lived oxosulfonium ion, 1-Ad-OS(CD3)2+, which can be characterized spectroscopically. This oxosulfonium ion reacts only slowly with water at elevated temperatures to give 1-adamantanol. DMSO is therefore a viable solvent for ks, kC, and kΔ cationic processes.

SOLVOLYSES OF alpha -KETO NORBORNYL TRIFLUOROACETATES AND TRIFLATES. DISCRETE alpha -KETO CATIONS VS. sigma -ASSISTED (k DELTA ) PROCESSES.

Trifluoroacetate derivatives of exo-2-hydroxy-endo-2-aryl bicyclo left bracket 2. 2. 1 right bracket heptan-3-ones have been prepared and solvolyzed in acetic acid. Small amounts of endo-trifluoroacetate products, via internal return, as well as major unr