F-BuOCl

The mechanism of the indolization of aniline 5 with methylthio-2-propanone 6 is illustrated below. Aniline 5 reacts with f-BuOCl to provide A-chloroaniline 9. This chloroaniline 9 reacts with sulfide 6 to yield azasulfonium salt 10. Deprotonation of the carbon atom adjacent to the sulfur provides the ylide 11. Intramolecular attack of the nucleophilic portion of the ylide 11 in a Sommelet-Hauser type rearrangement produces 12. Proton transfer and re-aromatization leads to 13 after which intramolecular addition of the amine to the carbonyl function generates the carbinolamine 14. Dehydration of 14 by prototropic rearrangement eventually furnishes the indole 8. 

Ca(0a)2 f-BuOCl, silica t-BuOCl, zeolites t-BuOCl, micelles R2NCX silica... 

Oxidation of (R)-(+)-2-iodo-a-methylbenzhydrol with f-BuOCl gives chiral chloro-A3-iodane, which on ligand exchange with NaN3 affords (+)-azido-A3-iodane [Eq. (6)] [26]. 

Many of these iodanes are formed by oxidation of ortho-iodobenzoic acids or certain orf/zo-iodophenylated alcohols with Cl2, AcOOH, f-BuOCl, CF3OF or magnesium monoperoxyphthalate. Among A3-iodanes more important are those derived from o-iodosobenzoic acid which is obtained from the mild oxidation of o-iodobenzoic acid. An improved yield for o-iodosobenzoic acid was obtained by hydrolysis of its acetyl derivative which in turn was prepared from o-iodobenzoic acid and acetyl nitrate in acetic anhydride, at room temperature (Scheme 14) [52]. 

The oxidation with [hydroxy(tosyloxy)iodo]benzene or other oxidants of the chiral alcohol o-IC6H4C(Me)(C6H5)OH is of interest because it provides a chiral benziodoxole (Scheme 16) with f-BuOCl a I-chloroiodane is formed first and then it undergoes substitution with nucleophiles [54]. 

Hydroxypyrazole 1-oxides are chlorinated at C4 using N-chlorosuc-cinimide (NCS) (1980JOC76) to give 4-chloro derivatives 215 (Hal1 = Cl), which can be further chlorinated at C4 using a second equivalent of NCS or f-BuOCl (1980JOC76). 

If methylcyclopropane is treated with f-BuOCl, various products are obtained, but the two major products are C and D. At lower temperatures more of C is formed and at higher temperatures more of D. 

HOC1, H20, CuC12 EtOCl / H20 f-BuOCl, H20, HOAc f-BuOCl, HOAc f-BuOCl, HOAc, H2S04 NaOCl, H20, C02 KOC1, H20, C02 Ca(OCl)2, HOAc, H20 Ca(OCl)2, C02, H20... 

Cl2, Ac20, NaOAc CI2, Ag02CR NCS, CF3C02H f-BuOCl, RC02H Cr02Cl2, AcCl AcOCl... 

Koizumi and co-workers used the optically active allylic chloroselenuranes bearing the 2-exo-hydroxyl-10-bornyl group to obtain optically active allylic amines [41]. The treatment of allylic selenides with f-BuOCl gave the corresponding allylic chloroselenuranes as the only product. Benzyl carbamate, t-butyl carbamate, p-tosylamide, and diphenylphosphinamide were selected as the AT-protected amines for selenimide formation. The nucleophilic reaction of... 

Diazoalkanes can also be converted to ethers by thermal or photochemical cleavage in the presence of an alcohol. These are carbene or carbenoid reactions. Similar intermediates are involved when diazoalkanes react with alcohols in the presence of f-BuOCl to give acetals. ... 

Reagents (a) dehydration, oxidation of trisubstituted olefin. Zone s oxidation, (b) l2,MeCN, (c) M-Bu3SnH, (d) cat.MsOH, (e) PhCOCl, toluene, (f) f-BuOCl (g) M-BuSnH, (h) Ph2-f-BuSiCl, DMAP, (i) LiOH, THF, (j) Swem oxidation (Me2SO, oxalyl chloride). 

Ca(OCl)2 f-BuOCl, silica f-BuOCl, zeolites f-BuOCl, micelles R2NC1, silica... 

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