Sulfonamides, alkylation azides

Mg or Ca in MeOH, " baker s yeast, Sm/l2, LiMe2NBH3, and tin complexes prepared from SnCl2 or Sn(SR)2. This reaction, combined with RX —+ RN3 (10-65), is an important way of converting alkyl halides RX to primary amines RNH2 in some cases the two procedures have been combined into one laboratory step. Sulfonyl azides (RSO2N3) have been reduced to sulfonamides (RSO2NH2) by irradiation in isopropyl alcohol and with NaH. ... 

Numerous methods to prepare individual classes of aliphatic diazo compounds have been extensively developed. The major strategies for their synthesis involve the alkaline cleavage of N-alkyl-N-nitroso-ureas, -carboxamides and -sulfonamides, dehydrogenation of hydrazones, as well as diazo group transfer from sulfonyl and related azides to active methylene compounds, and electrophilic diazoalkane substitution reactions. These synthetic methods have been comprehensively reviewed (15,16). Useful information on the preparation of selected diazo compounds can be found elsewhere (6,17). 

This reaction was initially reported by Dutt, Whitehead, and Wormall in 1921. It is the preparation of aromatic azide via the basic hydrolysis of aromatic diazoaminosulfinate that can be easily synthesized from aromatic diazonium salt and arylsulfonamide or alkyl-sulfonamide. Therefore, this reaction is known as the Dutt-Wormall reaction. Similarly, azides can be prepared via the cleavage of compounds from diazonium salt with ammonia, hydrazine," hydroxylamine, etc. 

N-[6-dimethylamino)-5-aryl(alkyl)-2-(trichloromethyl)pyrimidin-4-yl]-4-aryl(alkyl)sulfonamides 63 in moderate-to-good yields starting from terminal alkynes, sulfonyl azides, trichloroacetonitrile, and 1,1,3,3-tetramethylguanidine (Scheme 27) (13SL165). 

Coupling of (R)-IO and (R)-ll to (R)-12 is completed by the well-known Suzuki-Miyaura reaction where Pd(0) complex catalyzes the formation of the C-C bond (Sect. 6.3, Example 6.4). In the next step, the protecting group is eliminated and the C=C bond reduced by achiral Ir(I) complex to trans-(lR,4S)-14. It is important to note the wrong R configuration at the C(l) atom in this and the previous intermediate. Inversion of the configuration in (15,45)-15 is achieved by the Mitunobu reaction with diphenylphosphorylazide (dppa) as the source of nucleophilic azide ions in the presence of DBU. This reaction is the method of choice for the transformation of alcohols in many other functionalities, azides, esters, alkyl-aryl ethers, imides, sulfonamides, etc., and its mechanism is explained in considerable detail [21, 22]. 

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