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Highly Efficient Synthesis of Stereodefined Multisubstituted 1,4‐Dicyano‐ and 1‐Cyano‐1,3‐butadienes and Their Reactions with Organolithium Reagents
Author(s) -
Wang Congyang,
Wang Chao,
Wang Qifeng,
Wang Zhihui,
Sun Hui,
Guo Xiangyu,
Xi Zhenfeng
Publication year - 2007
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.200700028
Subject(s) - reagent , chemistry , stereoselectivity , combinatorial chemistry , tandem , pyrrole , electrophile , organolithium compounds , medicinal chemistry , organic chemistry , catalysis , materials science , composite material , ion , deprotonation
Stereodefined multisubstituted 1‐cyano‐ and 1,4‐dicyano‐1,3‐butadiene derivatives were obtained in excellent yields of the isolated product from their corresponding monohalo‐ and dihalobutadienes and CuCN. This reaction proceeded with high stereoselectivity and retention of the stereochemistry of the starting halobutadienes. A study of the utility of the thus‐obtained 1‐cyano‐ and 1,4‐dicyano‐1,3‐butadiene derivatives was demonstrated by their reactions with organolithium reagents. 2 H ‐Pyrrole or iminocyclopentadiene derivatives were formed in high yields from 1‐cyano‐4‐halo‐1,3‐butadienes and organolithium reagents. When 1,4‐dicyano‐1,3‐butadienes were treated with organolithium reagents followed by trapping with electrophiles, a tandem process took place to afford 2 H ‐pyrrolyl nitriles in excellent yields. Reduction of 1,4‐dicyano‐1,3‐butadiene derivatives with LiAlH 4 showed novel reaction patterns relative to normal nitriles.