Nucleophilic additions to polarized vinylarenes

TETRAHEDRON LETTERS

卷:57

Article

Gnanasekaran, Krishna Kumar¹  Yoon, Junghak¹  Bunce, Richard A.¹ 

[1] Oklahoma State Univ, Dept Chem, Stillwater, OK 74078 USA

关键词: Nucleophilic addition;    Polarized vinylarenes;    Hydroamination;    Reaction optimization;    Steric effects;   

DOI  :  10.1016/j.tetlet.2016.06.033

来源: Elsevier

【 摘 要 】

The addition of nucleophiles to the terminal double bond carbon of a styrene incorporating an electron withdrawing group at the ortho or para position has been studied. The conditions for this transformation have been optimized and structural modifications to the substrate have been explored. The structural changes included variation of the activating group on the aromatic ring and positioning substituents on the side chain double bond. The study revealed that nitro substitution gave the best results for addition of carbon and nitrogen nucleophiles. Cyano-substituted systems added carbon nucleophiles, but underwent polymerization or degradation with nitrogen nucleophiles. Ethoxycarbonyl-bearing substrates reacted primarily at the ester carbonyl. The reaction generally proceeded well with methyl on the a carbon of the double bond, but was slowed by methyl at the beta position. The yields varied from 50% to 97% for 22 examples. (C) 2016 Elsevier Ltd. All rights reserved.

【 授权许可】

Free