On February 20, 2004, Creary, Xavier; Burtch, Elizabeth A. published an article.COA of Formula: C7H14O3 The title of the article was Remarkably Facile Solvolyses of Triflates via Carbocationic Processes in Dimethyl Sulfoxide. And the article contained the following:
A number of triflates have been shown to undergo clean pseudo-first-order solvolysis reactions in DMSO-d6 to give products derived from carbocationic intermediates. Thus, t-BuCH(OTf)CO-t-Bu (5) and t-BuCH2OTf (9) react readily in DMSO-d6 at 25 °C to give a rearranged oxosulfonium salts, and subsequent alkene products where Me migration to the incipient cationic center occurs. t-BuCH(OTf)CO2CH3 (14) gives analogous rearranged products, and 1-methylcyclopropyl triflate (21) gives a ring-opened allylic oxosulfonium salt. These triflates react primarily via kΔ pathways. 6-Methylbicyclo[3.1.0]hex-6-yl triflate (23), bicyclo[2.2.1]hept-1-yl triflate (24), 1,6-methano[10]annulen-11-yl triflate (25), (CH3)2C(OTf)CO2CH3 (26), and (CH3)2CCN(OTf) (29) all react in DMSO-d6 to give carbocation-derived products. PhCH(OTf)CF3 (33) and substituted analogs also react readily in DMSO-d6, and the Hammett ρ+ value is -3.7. This suggests a “borderline” mechanism where the transition state has substantial charge development. The primary feature of these solvolyses is the high reactivity of all of these triflates in DMSO-d6. Thus, these triflates are all more reactive in DMSO-d6 than in HOAc, and for most, rates are faster than in CF3CH2OH. Triflates 5, 21, 29, and 33 are 108-109 times more reactive in DMSO-d6 than the corresponding mesylates. It is suggested that the decreased need for electrophilic solvation of triflate anion, and the high cation solvating ability of DMSO, are the reasons for the high triflate reactivity in DMSO-d6. The experimental process involved the reaction of Methyl 2-hydroxy-3,3-dimethylbutanoate(cas: 121129-31-5).COA of Formula: C7H14O3
The Article related to facile solvolysis triflate carbocation intermediate dimethyl sulfoxide solvent effect, Physical Organic Chemistry: Addition, Elimination, and Substitution Reactions and other aspects.COA of Formula: C7H14O3
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