622-93-5Relevant articles and documents
Iron-Catalyzed Anti-Markovnikov Hydroamination and Hydroamidation of Allylic Alcohols
Ma, Wei,Zhang, Xiaohui,Fan, Juan,Liu, Yuxuan,Tang, Weijun,Xue, Dong,Li, Chaoqun,Xiao, Jianliang,Wang, Chao
supporting information, p. 13506 - 13515 (2019/09/09)
Hydroamination allows for the direct access to synthetically important amines. Controlling the selectivity of the reaction with efficient, widely applicable, and economic catalysts remains challenging, however. This paper reports an iron-catalyzed formal anti-Markovnikov hydroamination and hydroamidation of allylic alcohols, which yields γ-amino and γ-amido alcohols, respectively. Homoallylic alcohol is also feasible. The catalytic system, consisting of a pincer Fe-PNP complex (1-4 mol %), a weak base, and a nonpolar solvent, features exclusive anti-Markovnikov selectivity, broad substrate scope (>70 examples), and good functional group tolerance. The reaction could be performed at gram scale and applied to the synthesis of drug molecules and heterocyclic compounds. When chiral substrates are used, the stereochemistry and enantiomeric excess are retained. Further application of the chemistry is seen in the functionalization of amino acids, natural products, and existing drugs. Mechanistic studies suggest that the reaction proceeds via two cooperating catalytic cycles, with the iron complex catalyzing a dehydrogenation/hydrogenation process while the amine substrate acts as an organocatalyst for the Michael addition step.
REDUCTIVE PREPARATION OF TERTIARY DIMETHYLAMINES FROM NITRILES
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Paragraph 0052; 0053, (2017/04/04)
This disclosure describes a low temperature process for the preparation of dimethyl amines from nitriles via reductive amination. In some embodiments, the process proceeds under mild conditions with aqeuous dimethylamine and show an unexpected rate acceleration by the inclusion of an acid addition salt of the dimethylamine.
Formation of 3-hydroxyalkyl carbamates from carbon dioxide, amines and oxetanes
Ishii, Shigeru,Zhou, Ming,Yoshida, Yasuhiko,Noguchi, Hiromichi
, p. 3207 - 3214 (2007/10/03)
The reactions of carbon dioxide, primary or secondary aliphatic amines and oxetanes at a CO2 pressure of 40 atm at 100-120°C without any catalysts afforded new monocarbamates of 1,3-propanediols, with concomitant formation of amino alcohols from oxetanes and amines.