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Base‐Promoted Double Amination of 1‐Haloalkynes: Direct Synthesis of Ene‐1,1‐diamines
Author(s) -
Gulia Nurbey,
Pigulski Bartłomiej,
Szafert Sławomir
Publication year - 2020
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.202000939
Subject(s) - chemistry , amination , steric effects , protonation , ene reaction , amine gas treating , diamine , salt (chemistry) , combinatorial chemistry , double bond , crystal structure , protecting group , stereochemistry , organic chemistry , polymer chemistry , catalysis , ion , alkyl
Selective and efficient synthetic procedure for highly reactive ene‐1,1‐diamines was developed by systematic investigation of double amination of 1‐haloalkynes. High yields, without the need for transition metal and simple isolation make the reported procedure superior compared to synthetic approaches reported so far. The reaction demonstrates high functional group tolerance, but its efficiency depends on the electronic properties of 1‐haloalkyne and the steric hindrance of an amine. The selected diamine and its corresponding protonated form – amidinium salt – have been examined for the first time by means of single‐crystal X‐ray diffraction. Finally, a new mechanism explaining selective formation of ene‐1,1‐diamines was proposed.