Methanesulfonamides

Li, catalytic naphthalene, -78°, THF, 97-99% yield. In addition, benzyl-amides and methanesulfonamides are efficiently cleaved. " ... 

Another point for structural diversification is the sulfonamide group. Imai had already shown that a wide variety of groups could be introduced at this position to optimize the reaction. Since a wide variety of sulfonyl chlorides are commercially available, a number of different types of groups could be examined (Scheme 3.34). Testing of a variety of aryl and alkyl groups on the 1,2-cyclohexanediamine backbone demonstrates that the simple methanesulfonamide 122 is clearly superior or equal to many other analogs in the cyclopropanation of cinnamyl alcohol (Table 3.11). Another concern which was directly addressed by this survey was the question of catalyst solubility. 

Employing protocol V with the methanesulfonamide catalyst 122, a 93 7 er can be obtained in the cyclopropanation of cinnamyl alcohol. This high selectivity translates well into a number of allylic alcohols (Table 3.12) [82]. Di- and tri-substi-tuted alkenes perform well under the conditions of protocol V. However, introduction of substituents on the 2 position leads to a considerable decrease in rate and selectivity (Table 3.12, entry 5). The major failing of this method is its inability to perform selective cyclopropanations of other hydroxyl-containing molecules, most notably homoallylic alcohols. 

The low rate of reaction for trisubstituted olefins was shown to be a result of slow hydrolysis of the osmium glycolate 29. However, this hydrolysis can be accelerated by a factor of up to 50 simply by the addition of methanesulfonamide.26 This modification permits the AD to be performed at lower temperature, which nearly always results in an increase in the stereoselectivity of the reaction.27... 

CN AJ-[4-[2-[Methyl[2-[4-[(methylsulfonyl)amino]phenoxy]ethyl]amino]ethyl]phenyl]methanesulfonamide... 

CN W-[4-[4-(ethylheptylamino)-l-hydroxybutyl]phenyl]methanesulfonamide ( )-2-butenedioate (2 1) (salt) base... 

CN iV-[4-[l-hydroxy-2-[(l-methylethyl)amino]ethyl]phenyl]methanesulfonamide monohydrochloride... 

Scheme 9 a TBDMSiCl2, imidazole, CH2CI2 AD mix a (Sharpless asymmetric dihydrox-ylation reagent), methanesulfonamide, H20/t-butyl alcohol b NaOCl, KBr, TEMPO in CH2C12/H20 c NH2OH HCl, pyridine/EtOH, 90 °C d NaOH, 1,2-propanediol, 160 °C e PPh3, DIAD, toluene, 0 °C, reflux [54]... 

Cerium(m) chloride could mediate high-yielding additions of /V-bcnzyl- ,/V-dilithio methanesulfonamide 12 to aldehydes and ketones of biologically importance (Scheme 5).9 Excess amount of CeCl3 (8.2 equiv.) afforded the adduct in excellent yield, while lower yield of the adduct was obtained in the absence of CeCl3. 

With sulfonamide-derived chloramine salts bearing smaller organic substituents on the sulfur, for example, methanesulfonamide-derived chloramine salt 111 (chloramine-M) as the oxidant, better results are obtained. This reagent can be prepared separately and added to the reaction mixture as the stable anhydrous... 

In a 250 mL round-bottomed flask equipped with a magnetic stirrer bar were placed a 1 1 mixture of tert-butanol and water (140 mL), AD-mix- 3 (20 g) and methanesulfonamide (1.36 g) S. ... 

AT-Alkyl methanesulfonamides, 23 685 Alkyl monoperoxycarbonic acid, 18 466 Alkylnaphthalenes, 17 84-85 dispersant moieties, 8 706t Alkyl naphthalene sulfonates, 24 146 Alkylnickel, re-complexes of, 17 116 Alkyl nitrites, formation of, 17 165-166 Alkylonium salt hydrates, 14 171... 

Methane refrigeration system, 10 617 Methanesulfonamide, 23 684 Methanesulfonate esters, 23 682 Methanesulfonic acid, 15 168 23 681-685 metal salts of, 23 684... 

Ortho eliminations find widespread application in the structure elucidation of aromatic nitro compounds, e.g., nitroanilines, [200] dinitrophenols, [213] trini-troaromatic explosives, [214] and nitrophenyl-methanesulfonamides. [199] (Scheme 6.75 reproduced from Ref. [199] with permission. IM Publications 1997) ... 

Danikiewicz, W. Ortho Interactions During Fragmentation of N- 2-Nitrophenyl)methanesulfonamide and Its N-Alkyl Derivatives Upon Electron Ionization. Eur. Mass Spectrom. 1997, 3, 209-216. 

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