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Development of Highly Chemoselective Bulky Zincate Complex, t Bu 4 ZnLi 2 : Design, Structure, and Practical Applications in Small‐/Macromolecular Synthesis
Author(s) -
Furuyama Taniyuki,
Yonehara Mitsuhiro,
Arimoto Sho,
Kobayashi Minoru,
Matsumoto Yotaro,
Uchiyama Masanobu
Publication year - 2008
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.200800536
Subject(s) - zincate , dilithium , chemistry , halogen , propargyl bromide , chemoselectivity , electrophile , reagent , propargyl , zinc , amide , polymer chemistry , lithium amide , bromide , combinatorial chemistry , organic chemistry , alkyl , ion , enantioselective synthesis , deprotonation , catalysis
We present full details of the unique reactivities of the newly developed dianion‐type bulky zincate, dilithium tetra‐ tert ‐butylzincate ( t Bu 4 ZnLi 2 ). With this reagent, halogen–zinc exchange reaction of variously functionalized haloaromatics and anionic polymerization of N ‐isopropylacrylamide (NIPAm)/styrene with excellent chemoselectivity were realized. Halogen–zinc exchange reaction followed by electrophilic trapping with propargyl bromide provided a convenient route to functionalized phenylallenes, particularly those with electrophilic functional groups (such as cyano, amide and halogens). Spectral and computational studies of the structure in the gas and liquid phases indicated extraordinary stabilization of this dianion‐type zincate by its bulky ligands.