Development of Highly Chemoselective Bulky Zincate Complex, tBu4ZnLi2: Design, Structure, and Practical Applications in Small-/Macromolecular

被引：74

作者：

Furuyama, Taniyuki ^{[1
,2
]}

Yonehara, Mitsuhiro ^{[1
,2
]}

Arimoto, Sho ^{[2
]}

Kobayashi, Minoru ^{[3
]}

Matsumoto, Yotaro ^{[2
]}

Uchiyama, Masanobu ^{[1
,2
]}

机构：

[1] RIKEN, Adv Elements Chem Lab, Wako, Saitama 3510198, Japan

[2] Univ Tokyo, Grad Sch Pharmaceut Sci, Bunkyo Ku, Tokyo 1130033, Japan

[3] Japan Sci & Technol Corp JST, PRESTO, Tokyo, Japan

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2008年 / 14卷 / 33期

关键词：

chemoselective metalation; halogen-metal exchange; nucleophilic substitution; polymerization; zinc;

D O I：

10.1002/chem.200800536

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

We present full details of the unique reactivities of the newly developed dianion-type bulky zincate, dilithium tetra-tert-butylzincate (tB(4),ZnLi2). With this reagent, halogen-zine exchange reaction of variously functionalized haloaromatics and anionic polymerization of N-isopropyl-acrylamide (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.

引用

页码：10348 / 10356

页数：9

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