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Regioselective Ring Opening Reactions of Pyridine N-Oxide Analogues by Magnesium Hydride Complexes
Organometallics ( IF 2.5 ) Pub Date : 2017-09-01 00:00:00 , DOI: 10.1021/acs.organomet.7b00517
Hongyan Xie 1, 2 , Xinli Liu 1 , Dongmei Cui 1
Affiliation  

The stoichiometric reactions of phosphinimino-amino (PIA)-supported magnesium hydride complex 1, [L1MgH]2 (L1 = (2,6-iPr2-C6H3)NC(Me)CHP(Cy2)N(2,6-Me2-C6H3)), with pyridine N-oxide and 2-phenylpyridine N-oxide afforded 2,4-pentadiene-1-oximate complex 2 and 5-phenyl-2,4-pentadiene-1-oximate complex 3, respectively. The reaction of 1 with 2-methylpyridine N-oxide showed a unique regioselectivity to produce 2,4-hexadiene-1-oximate 4a in toluene and 3,5-hexadiene-2-oximate 4b in THF, respectively. Treatment of β-diketiminato (BDI)-supported magnesium hydride complex 5, [L2MgH]2 (L2 = (2,6-iPr2-C6H3)NC(Me)CHC(Me)N(2,6-iPr2-C6H3)), with quinoline N-oxide gave 1,2-dihydroquinoline type product 6, while treatment of complex 5 with 2-methylpyridine N-oxide either in toluene or THF afforded 1-methyl-2,4-pentadiene-1-oximate complex 7 as the only product. All these complexes were fully characterized by NMR spectroscopy and X-ray diffraction analyses, and mechanism researches were conducted to understand the ring-opening reaction of pyridine N-oxide.

中文翻译:

氢化镁配合物的吡啶N-氧化物类似物的区域选择性开环反应

磷氨基氨基(PIA)负载的氢化镁配合物1,[L 1 MgH] 2(L 1 =(2,6- i Pr 2 -C 6 H 3)NC(Me)CHP(Cy 2)的化学计量反应N(2,6-Me 2 -C 6 H 3)),用吡啶N-氧化物和2-苯基吡啶N-氧化物得到2,4-戊二烯-1-肟酸酯络合物2和5-苯基-2,4-戊二烯-1-肟酸络合物31与2-甲基吡啶N的反应-氧化物显示出独特的区域选择性,以分别在甲苯中产生2,4-己二烯-1-肟基酯4a和在THF中产生3,5-己二烯-2-肟基酯4b。β-二酮基亚氨基(BDI)负载的氢化镁复合物5,[L 2 MgH] 2(L 2 =(2,6- i Pr 2 -C 6 H 3)NC(Me)CHC(Me)N(2)的处理,6- i Pr 2 -C 6 H 3)),用喹啉N-氧化物得到1,2-二氢喹啉型产物6,同时用2-甲基吡啶处理配合物5在甲苯或THF中的N-氧化物提供作为唯一产物的1-甲基-2,4-戊二烯-1-肟酸酯络合物7。通过NMR光谱和X射线衍射分析充分表征了所有这些配合物,并进行了机理研究以了解吡啶N-氧化物的开环反应。
更新日期:2017-09-04
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