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首页> 外文期刊>The Journal of Organic Chemistry >CATALYTIC IRON-MEDIATED ENEDIENE CARBOCYCLIZATIONS - INVESTIGATIONS INTO THE STEREOSELECTIVE FORMATION OF BICYCLIC RING SYSTEMS
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CATALYTIC IRON-MEDIATED ENEDIENE CARBOCYCLIZATIONS - INVESTIGATIONS INTO THE STEREOSELECTIVE FORMATION OF BICYCLIC RING SYSTEMS

机译:催化铁介导的二烯碳环化-对双环系统立体选择形成的研究

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摘要

Trienes in which the requisite 1,3-diene and allylic ether moieties are appended to a pre-existing ring system afford bicyclic ring systems-upon iron-catalyzed cyclization. The efficiency and stereoselectivity of the cyclization are dramatically influenced by the nature of the ring system to which the diene and alkene subunits are appended. Certain bicyclic ring systems are formed in good yield; most notably, substrates bearing a basic nitrogen are well-tolerated and certain indolizidine and quinolizidine ring systems are accessible using this methodology. The efficiency and stereoselectivity of the cyclization is also markedly dependent on the ligand used to modify the iron catalyst, and in this regard, a bisoxazoline-modified iron catalyst system is generally superior to what was the standard bipyridine-modified catalyst. In the course of these studies a difference spin polarization transfer (DSPT) experiment proved very useful for the stereochemical analysis of compounds that exhibit very crowded high field NMR spectra. [References: 54]
机译:将必要的1,3-二烯和烯丙基醚部分连接到预先存在的环系统上的三烯在铁催化的环化反应中提供双环系统。环化的效率和立体选择性受到二烯和烯烃亚基附加于其上的环系统的性质的显着影响。某些双环系统以高收率形成;最值得注意的是,带有碱性氮的底物具有良好的耐受性,并且使用这种方法可以达到某些吲哚并咪唑和喹喔啉环系统。环化的效率和立体选择性还明显取决于用于修饰铁催化剂的配体,就此而言,双恶唑啉改性的铁催化剂体系通常优于标准联吡啶改性的催化剂。在这些研究过程中,差异自旋极化转移(DSPT)实验证明对显示非常拥挤的高场NMR光谱的化合物的立体化学分析非常有用。 [参考:54]

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