Synthesis, Structure, and Catalytic Activity of TiIV and ZrIV Complexes Derived from (R)‐2,2′‐Diamino‐1,1′‐binaphthyl‐Based N4‐Donor Ligands
Synthesis, Structure, and Catalytic Activity of TiIV and ZrIV Complexes Derived from (R)‐2,2′‐Diamino‐1,1′‐binaphthyl‐Based N4‐Donor Ligands
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DOI：
10.1002/ejic.200701105
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发表时间：
2008-03
影响因子：
2.3
通讯作者：
Li Xiang;Hai-bin Song;Guofu Zi
中科院分区：
文献类型：
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作者：
Li Xiang;Hai-bin Song;Guofu Zi
将（R）-双（吡咯-2-基亚甲基氨基）-1，1 '-联萘（1H 2）或（R）-N，N'-双（吡啶-2-基甲基）-1，1 '-联萘-2，2'-二胺（2 H2）与Zr（NMe 2）4（1当量）反应，以较好的产率分别得到手性氨基锆1-Zr（NMe 2）2·C7 H8（4·C7 H8）和2-Zr（NMe 2）2（6）。在类似的条件下，1H 2与Ti（NMe 2）4（1当量）反应。以得到手性氨基钛1-Ti（NMe 2）2·C6 H6（3·C6 H6），而用Ti（NMe 2）4（1当量）处理2 H2则得到手性氨基钛1-Ti（NMe 2）2·C6 H6（3·C6 H6）。以74%的产率分离出双（连接）产物（2）2-Ti·C7 H8（5·C7 H8）。所有的配合物，其特征在于通过各种光谱技术，元素分析，和X-射线衍射分析。氨基化锆4和6是用于氨基烯烃的不对称氢胺化/环化的活性催化剂，并且以良好至优异的产率获得具有中等ee值（高达59%）的环胺;氨基化钛2和5在反应条件下没有活性。（© Wiley-VCH Verlag GmbH & Co. KGaA，69451魏因海姆，德国，2008）
Reaction of (R)-bis(pyrrol-2-ylmethyleneamino)-1,1′-binaphthyl (1H2) or (R)-N,N′-bis(pyridin-2-ylmethyl)-1,1′-binaphthyl-2,2′-diamine (2H2) with Zr(NMe2)4 (1 equiv.) gives chiral zirconium amides 1-Zr(NMe2)2·C7H8 (4·C7H8) or 2-Zr(NMe2)2 (6) in good yields, respectively. Under similar conditions, 1H2 reacts with Ti(NMe2)4 (1 equiv.) to give chiral titanium amide 1-Ti(NMe2)2·C6H6 (3·C6H6), whereas treatment of 2H2 with Ti(NMe2)4 (1 equiv.) leads to the isolation of bis(ligated) product (2)2-Ti·C7H8 (5·C7H8) in 74 % yield. All complexes were characterized by various spectroscopic techniques, elemental analysis, and X-ray diffraction analysis. Zirconium amides 4 and 6 are active catalysts for the asymmetric hydroamination/cyclization of aminoalkenes, and cyclic amines were obtained in good-to-excellent yields with moderate ee values (up to 59 %); titanium amides 2 and 5 were not active under the reaction conditions. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)