A radical thia-Brook rearrangement.
نویسندگان
چکیده
Geminal mercapto trialkyl- and trialkoxy-silanes undergo an efficient radical chain rearrangement, whereby the silyl group migrates from carbon to sulfur; the starting materials are readily obtained by exploiting the peroxide initiated radical addition of dithiocarbonates (xanthates) to trialkyl- or trialkoxy-vinylsilanes.
منابع مشابه
The [1,5]-Brook rearrangement: an initial application in anion relay chemistry.
The [1,5]-Brook rearrangement proceeds efficiently in a series of hydroxyl dithiane substrates with sodium and potassium bases; less effective are lithium bases. That the mode of silyl migration is intramolecular was demonstrated by a crossover experiment. Finally, the tricomponent anion relay chemistry (ARC) coupling tactic was demonstrated employing the [1,5]-Brook rearrangement.
متن کاملUnanticipated formation of ortho-sulfone substituted phenols by anionic thia-Fries rearrangement of (aryl triflate)tricarbonylchromium complexes.
Tricarbonylchromium complexes of aryl triflates undergo base-mediated anionic thia-Fries rearrangements to generate push-pull substituted [ortho-hydroxyaryl(trifluoromethylsulfonyl)phenol]tricarbonylchromium complexes under very mild reaction conditions.
متن کاملTandem thia-Fries rearrangement--cyclisation of 2-(trimethylsilyl)phenyl trifluoromethanesulfonate benzyne precursors.
A novel transformation of 2-(trimethylsilyl)phenyl trifluoromethanesulfonate aryne precursors is described.
متن کاملReversal of facial selectivity in a thia-Claisen rearrangement by incorporation of a vinylic bromine substituent.
Thia-Claisen rearrangements have been carried out using N-benzylpyrrolidine-2-thione and chiral allylic bromides derived from D-mannitol. Introduction of a bromine atom onto the double bond of the allylic bromide reverses the sense of diastereoselectivity in the [3,3]-sigmatropic rearrangement. Density functional theory calculations lead us to rationalise the observed selectivity in terms of a ...
متن کاملThia-bridged triarylamine heterohelicene radical cations as redox-driven molecular switches.
The first example of one-electron oxidation of thia-bridged triarylamine heterohelicenes to the corresponding exceptionally stable radical cations, fully characterized, as hexafluoroantimonate salts, by means of UV-Vis, EPR, ENDOR, density functional theory calculations and X-ray analyses, is reported. Chemical and electrochemical reversible redox processes are solidly demonstrated.
متن کاملذخیره در منابع من
با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید
برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید
ثبت ناماگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید
ورودعنوان ژورنال:
- Chemical communications
دوره 50 45 شماره
صفحات -
تاریخ انتشار 2014