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Investigations of Different Chemoselectivities in Primary, Secondary and Tertiary Amide Reactions with Sodium Borohydride
Author(s) -
Ren Jie,
Li LiangChun,
Liu JiKai,
Zhu HuaJie,
Pittman Charles U.
Publication year - 2006
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.200500834
Subject(s) - chemistry , sodium borohydride , amide , primary (astronomy) , nitrile , acetonitrile , medicinal chemistry , borohydride , hydride , sodium hydride , hydrogen atom abstraction , sodium , inorganic chemistry , hydrogen , organic chemistry , catalysis , physics , astronomy
The mechanisms for the different chemoselectivities in sodium borohydride reactions with primary, secondary and tertiary amides have been investigated both at the B3LYP/6‐31++G(d,p)//B3LYP/6‐31G(d,p) and B3LYP/6‐31++G(d,p)//HF/6‐31G(d,p) levels of theory. The predicted structures of the key intermediates were then confirmed by experiments. Primary amides generate the corresponding nitriles when treated with sodium borohydride. Nitrile formation occurs by initial proton abstraction from the primary amide’s nitrogen atom by a hydride ion, followed by loss of hydrogen and the coordination of the amide nitrogen atom to BH 3 . Three subsequent steps produce acetonitrile. The computational predictions agree well with the experimental results. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)