Ar are reductive coupling of nitro compounds with organohalides has been realized. The reaction is initiated by ap artial reduction of the nitro group to an itrenoid intermediate.T herefore,n ot only aromatic but also aliphatic nitro compounds are efficiently transformed into monoalkylated amines,w ith organohalides as the alkylating agent. Given the innate reactivity of the nitrenoid, ac atalyst is not required, resulting in ahigh tolerance for aryl halide substituents in both starting materials. Scheme 1. Reductivec oupling strategies. Table 2: Scope of the reductive coupling of nitro compounds with organohalides.Reaction conditions: Zn powder (4 equiv) and LiCl (2.2 equiv) were dried in vacuo, 1mLTHF was added, followed by pretreatment with catalytic amounts of TMSCl and dibromoethane. R 1 X 2 (0.6 mmol, 3equiv), the nitro compound 1 (0.2 mmol), and B 2 pin 2 (0.4 mmol, 2equiv) were added and the reaction was stirred for 12 hatRT. The aminoborane D was hydrolyzed by addition of water.[a] Carried out at 50 8 8C.[b] Reaction stirred for 1hat 50 8 8Cbefore the addition of 1a.[c] Carried out at 70 8 8C. Structures, compound numbers, and yields of isolatedproducts after column chromatography are given.
A rare reductive coupling of nitro compounds with organohalides has been realized. The reaction is initiated by a partial reduction of the nitro group to a nitrenoid intermediate. Therefore, not only aromatic but also aliphatic nitro compounds are efficiently transformed into monoalkylated amines, with organohalides as the alkylating agent. Given the innate reactivity of the nitrenoid, a catalyst is not required, resulting in a high tolerance for aryl halide substituents in both starting materials.
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