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Synthesis of ( Z )‐β‐(Carbonylamino)alkenylindium through Regioselective anti ‐Carboindation of Ynamides and Its Transformation to Multisubstituted Enamides
Author(s) -
Kang Kyoungmin,
Sakamoto Kosuke,
Nishimoto Yoshihiro,
Yasuda Makoto
Publication year - 2020
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201905175
Subject(s) - ketene , regioselectivity , nucleophile , silylation , chemistry , halogenation , transformation (genetics) , combinatorial chemistry , medicinal chemistry , catalysis , organic chemistry , biochemistry , gene
The regioselective anti ‐carboindation of ynamides by using InBr 3 and silylated nucleophiles was developed to synthesize ( Z )‐β‐(carbonylamino)alkenylindiums. The X‐ray crystallographic analysis of an alkenylindium suggested that the reaction proceeded in an anti ‐addition fashion. In contrast to reported syn ‐carbometalations of ynamides by using organometallics, a cooperation of InBr 3 and silylated nucleophiles to ynamides achieved an anti ‐addition, which was supported by DFT calculations. The scope of substrates included various ynamides and silylated nucleophiles, such as silyl ketene acetals and silyl ketene imines. The transformation of synthesized alkenylindiums by iodination, radical coupling, and Pd‐catalyzed cross‐coupling successfully afforded trisubstituted enamines with high regio‐ and stereoselectivities.