770-69-4Relevant articles and documents
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Tabushi,I.,Fukunishi,K.
, p. 3748 - 3750 (1974)
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Direct Deamination of Primary Amines via Isodiazene Intermediates
Berger, Kathleen J.,Driscoll, Julia L.,Yuan, Mingbin,Dherange, Balu D.,Gutierrez, Osvaldo,Levin, Mark D.
supporting information, p. 17366 - 17373 (2021/11/04)
We report here a reaction that selectively deaminates primary amines and anilines under mild conditions and with remarkable functional group tolerance including a range of pharmaceutical compounds, amino acids, amino sugars, and natural products. An anomeric amide reagent is uniquely capable of facilitating the reaction through the intermediacy of an unprecedented monosubstituted isodiazene intermediate. In addition to dramatically simplifying deamination compared to existing protocols, our approach enables strategic applications of iminium and amine-directed chemistries as traceless methods. Mechanistic and computational studies support the intermedicacy of a primary isodiazene which exhibits an unexpected divergence from previously studied secondary isodiazenes, leading to cage-escaping, free radical species that engage in a chain, hydrogen-atom transfer process involving aliphatic and diazenyl radical intermediates.
Halogen Exchange Reaction of Aliphatic Fluorine Compounds with Organic Halides as Halogen Source
Mizukami, Yuki,Song, Zhiyi,Takahashi, Tamotsu
supporting information, p. 5942 - 5945 (2016/01/09)
The halogen exchange reaction of aliphatic fluorine compounds with organic halides as the halogen source was achieved. Treatment of alkyl fluorides (primary, secondary, or tertiary fluorides) with a catalytic amount of titanocene dihalides, trialkyl aluminum, and polyhalomethanes (chloro or bromo methanes) as the halogen source gave the corresponding alkyl halides in excellent yields under mild conditions. In the case of a fluorine/iodine exchange, no titanocene catalyst is needed. Only C-F bonds are selectively activated under these conditions, whereas alkyl chlorides, bromides, and iodides are tolerant to these reactions.