Aromatic Metamorphosis of Thiophenes by Means of Desulfurative Dilithiation.

作者: Atsushi Kaga , Hirokazu Iida , Shun Tsuchiya , Hayate Saito , Koji Nakano

DOI: 10.1002/CHEM.202005223

关键词: Lithium metalDouble bondThiopheneHeteroatomLithiumCombinatorial chemistryChemistryBenzeneSulfurElectrophile

摘要: A new mode of aromatic metamorphosis has been developed, which allows thiophenes and their benzo-fused derivatives to be converted a variety exotic heteroles. This transformation involves 1) the efficient generation key 1,4-dianions by means desulfurative dilithiation with lithium powder 2) the subsequent trapping the dianions heteroatom electrophiles in one-pot manner. Via dilithiation, sulfur atoms are replaced also carbon-carbon double bond or 1,2-phenylene for construction benzene rings.

参考文章(105)
Shaoguang Zhang, Wen-Xiong Zhang, Zhenfeng Xi, Organo-di-Lithio Reagents: Cooperative Effect and Synthetic Applications Organo-di-Metallic Compounds (or Reagents). pp. 1- 41 ,(2013) , 10.1007/3418_2013_71
Chao Wang, Qian Luo, Hui Sun, Xiangyu Guo, Zhenfeng Xi, Lithio Siloles: Facile Synthesis and Applications Journal of the American Chemical Society. ,vol. 129, pp. 3094- 3095 ,(2007) , 10.1021/JA070404S
Chanjuan Xi, Shouquan Huo, Tarek Hassan Afifi, Ryuichiro Hara, Tamotsu Takahashi, Remarkable effect of copper chloride on diiodination of zirconacyclopentadienes Tetrahedron Letters. ,vol. 38, pp. 4099- 4102 ,(1997) , 10.1016/S0040-4039(97)00835-6
Qian Luo, Chao Wang, Li Gu, Wen-Xiong Zhang, Zhenfeng Xi, Formation of α‐Lithio Siloles from Silylated 1,4‐Dilithio‐1,3‐Butadienes: Mechanism and Applications Chemistry-an Asian Journal. ,vol. 5, pp. 1120- 1128 ,(2010) , 10.1002/ASIA.200900287
Stephen L. Buchwald, Ralph B. Nielsen, Selective, zirconium-mediated cross-coupling of alkynes: the synthesis of isomerically pure 1,3-dienes and 1,4-diiodo-1,3-dienes Journal of the American Chemical Society. ,vol. 111, pp. 2870- 2874 ,(1989) , 10.1021/JA00190A021
Shigehiro Yamaguchi, Yujiro Itami, Kohei Tamao, Group 14 Metalloles with Thienyl Groups on 2,5-Positions: Effects of Group 14 Elements on Their π-Electronic Structures† Organometallics. ,vol. 17, pp. 4910- 4916 ,(1998) , 10.1021/OM980393Z
Zhengkun Yu, John G. Verkade, Desulfurization of organosulfur compounds with lithium and sodium Energy & Fuels. ,vol. 13, pp. 23- 28 ,(1999) , 10.1021/EF9800260
Zhenfeng Xi, 1,4-Dilithio-1,3-dienes: reaction and synthetic applications. Accounts of Chemical Research. ,vol. 43, pp. 1342- 1351 ,(2010) , 10.1021/AR1000583