Highly efficient synthesis of stereodefined multisubstituted 1,4-dicyano- and 1-cyano-1,3-butadienes and their reactions with organolithium reagents.
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. 2H-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 2H-pyrrolyl nitriles in excellent yields. Reduction of 1,4-dicyano-1,3-butadiene derivatives with LiAlH4 showed novel reaction patterns relative to normal nitriles.
Wang
Congyang
C
Beijing National Laboratory for Molecular Sciences (BNLMS), Ministry of Education, College of Chemistry, Peking University, Beijing 100871, China.
Wang
Chao
C
Wang
Qifeng
Q
Wang
Zhihui
Z
Sun
Hui
H
Guo
Xiangyu
X
Xi
Zhenfeng
Z
D002070:Butadienes / Q000138:chemical synthesis / Q000737:chemistry*; D008094:Lithium / Q000737:chemistry*; D009570:Nitriles / Q000138:chemical synthesis / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry; D013237:Stereoisomerism
D002070:Butadienes; D009570:Nitriles; D009942:Organometallic Compounds; D008094:Lithium