Alkylating Agents Stronger than Alkyl Triflates Научная публикация
Журнал |
Journal of the American Chemical Society
ISSN: 0002-7863 , E-ISSN: 1520-5126 |
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Вых. Данные | Год: 2004, Том: 126, Номер: 39, Страницы: 12451-12457 Страниц : 7 DOI: 10.1021/ja047357d | ||||||
Ключевые слова | Aromatic hydrocarbons; Catalysts; Chemical bonds; Crystal structure; Extraction; Halogen compounds; Isomers; Reaction kinetics; Salts | ||||||
Авторы |
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Организации |
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Реферат:
A new class of potent electrophilic “R+ ” alkylating agents has been developed using weakly nucleophilic carborane anions as leaving groups. These reagents, R(CHB11Me5X6) (R = Me, Et, and i-Pr; X = Cl, Br), are prepared via metathesis reactions with conventional alkylating agents such as alkyl triflates, using the high oxophilicity of silylium ion-like species, Et3Si(carborane), as the driving force to obtain increased alkyl electrophilicity. The crystal structure of the isopropyl reagent, i-Pr(CHB11Me5Br6), has been determined, revealing covalence in the alkyl−carborane bonding. This contrasts with the free i-Pr+ carbocation observed when the anion is less coordinating (e.g. Sb2F11-) or with tertiary alkyl centers, as in [tert-butyl][carborane] salts. In solution, the reagents exist as equilibrating isomers with the alkyl group at the 7−11 or 12 halide positions of the CB11 icosahedral carborane anion. These alkylating agents are so electrophilic that they (a) react with alkanes at or below room temperature via hydride extraction to produce carbenium ions, (b) alkylate benzene without a Friedel−Crafts catalyst to give arenium ions, and (c) alkylate electron-deficient phosphorus compounds that are otherwise inert to conventional alkylating agents such as methyl triflate.
Библиографическая ссылка:
Kato T.
, Stoyanov E.
, Geier J.
, Grützmacher H.
, Reed C.A.
Alkylating Agents Stronger than Alkyl Triflates
Journal of the American Chemical Society. 2004. V.126. N39. P.12451-12457. DOI: 10.1021/ja047357d WOS Scopus РИНЦ
Alkylating Agents Stronger than Alkyl Triflates
Journal of the American Chemical Society. 2004. V.126. N39. P.12451-12457. DOI: 10.1021/ja047357d WOS Scopus РИНЦ
Файлы:
Полный текст от издателя
Даты:
Поступила в редакцию: | 5 мая 2004 г. |
Опубликована online: | 11 сент. 2004 г. |
Опубликована в печати: | 1 окт. 2004 г. |
Идентификаторы БД:
Web of science | WOS:000224219900066 |
Scopus | 2-s2.0-4644252938 |
РИНЦ | 13451193 |
Chemical Abstracts | 2004:742139 |
Chemical Abstracts (print) | 141:410981 |
OpenAlex | W2042644399 |