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Hydroaminocarbonylation of Alkynes to Produce Primary α , β ‐Unsaturated Amides Using NH 4 HCO 3 Dually as Ammonia Surrogate and Brønsted Acid Additive
Author(s) -
Wang DongLiang,
Guo WenDi,
Zhou Qing,
Liu Lei,
Lu Yong,
Liu Ye
Publication year - 2018
Publication title -
chemcatchem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.497
H-Index - 106
eISSN - 1867-3899
pISSN - 1867-3880
DOI - 10.1002/cctc.201800791
Subject(s) - catalysis , chemistry , ammonia , brønsted–lowry acid–base theory , phenylacetylene , hydrolysis , primary (astronomy) , hydrazoic acid , medicinal chemistry , nitrogen , dehydration , organic chemistry , physics , astronomy , biochemistry
By using NH 4 HCO 3 dually as ammonia surrogate and Brønsted acid additive, the production of primary α,β ‐unsaturated amides via hydroaminocarbonylation of alkynes was accomplished efficiently. The advantages of using the solid and inexpensive NH 4 HCO 3 included: (1) the facile and clean manipulation without presence of stinky gaseous NH 3 or liquids organic amines, (2) the inhibition of the subsequent dehydration and hydrolysis of amides due to its weak basicity, and (3) the facilitated formation of Pd−H catalytic active species by the released H 2 CO 3 serving as a weak Brønsted acid additive. In addition, the diphopshine of Dppp with the natural bite angle ( β n ) of 91° was found indispensable to spur the performance of the palladium catalyst for this reaction. Both terminal and internal phenylacetylene derivatives could be used as the substrates, affording the corresponding primary α,β ‐unsaturated amides in good yields along with excellent regio‐selectivities to the branched ones.