Chloroamination alkenes

The groups R2N and Cl can be added directly to alkenes, allenes, conjugated dienes, and alkynes, by treatment with dialkyl-V-chloroamines and acids. " These are free-radical additions, with initial attack by the R2NH- radical ion. " N-Halo amides (RCONHX) add RCONH and X to double bonds under the influence of UV light or chromous chloride. " Amines add to allenes in the presence of a palladium catalyst. ... 

Aziridination of alkenes can be carried out using N-(p- to I ucncsu I I o n y I i m i n o) phenyliodinane and copper triflate or other copper salts.257 These reactions are mechanistically analogous to metal-catalyzed cyclopropanation. Rhodium acetate also acts as a catalyst.258 Other arenesulfonyliminoiodinanes can be used,259 as can chloroamine T260 and bromoamine T.261 The range of substituted alkenes that react includes acrylate esters.262... 

Dioxazolidines are produced by cyclization of A,A-dialkoxy- or A -alkoxy-A -chloroamines (Scheme 11) <93CRV725>. The synthetic potential of this method far surpasses that of the photochemical addition of nitrobenzene to alkenes <84CHEC-1(6)-914). 

Zefirov and coworkers have developed procedures for chlorosulfamation of alkenes and alkynes using reagents of the type R2NSO2OCI formed by insertion of sulfur trioxide into the nitrogen-chlorine bond in yV-chloroamines (R2NCI).106... 

Radical chloroaminations are known, using radical, transition metal ion or photochemical initiation. They also occur without overt initiation, thus anti-Markovnikov additions to terminal alkenes occur with N,N-dichlorourethane in benzene at 5-40 C (yields <= 60%)P Similar reactions occur with N,N-dichlo-roarenesulfonamides in CH2CI2 at or below room temperature (yields mostly 53-91% 10% with isobu-tylene). ° The remaining N—Cl bond is reaiUly reduced if desired with sodium sulflte. N-Halosulfoximines also add to alkenes thermally or photolytically. ... 

Very strongly electrophilic radicals are the amino radical cations, RaNH, which can be easily obtained from N-chloroamines they are very versatile and react differently with alkanes >, alkenes alk5mes and aromatics involving potentially most of the organic compounds and showing in all cases an exceptional sensitivity to polar effects. 

Synthesis of Al-Chloroamines. The conversion of secondary amines to iV-chloroamines by reaction with NCS in ether or dichloromethane has many advantages over the use of aqueous hypochlorite, including ease of isolation. This method has been used repeatedly in the preparation of Al-chloroamines for alkene amination (eqs 12 and 13) and other reactions. ... 

A-Chloroamines (e.g. 14), on treatment with strong bases such as potassium Fbutoxide or lithium diisopropylamide (LDA), give 2-aza-allyl anions (15) that can undergo r4s -I- tt2s cycloadditions with alkenes to give pyrrolidines. Imines can also be accessed by dehydrochlorination of (14), under modified conditions. ... 

Further examples of the Ritter reaction(cf. section IV.B) are provided by the many substituted olefins that may be protonated to ve carbonium ions which can be intercepted by hydrogen cyanide or organic nitriles cyanogen chloride can also be used as intercepting species , but offers no advantages. Mixtures of the two possible amides, and hence amines, are to be expected from non-terminal alkenes and from such olefinic compounds as oleic acid Olefins may also be converted to amines with yields of up to 60%, by hydroboration and subsequent reaction of the organoborane with chloroamine in alkaline solution or preferably with hydroxylamine-0-sulphonic acid in diglyme (reaction 86) The reaction is applicable... 

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