Addition of thianthrene cation radical to cycloalkenes. An unexpected monoadduct
Addition of thianthrene cation radical to cycloalkenes. An unexpected monoadduct
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DOI：
10.1021/jo9911241
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发表时间：
1999-12-10
影响因子：
3.6
通讯作者：
Whitmire, KH
中科院分区：
文献类型：
--
作者：
Lee, WK;Liu, B;Whitmire, KH
而硫杂菲阳离子基高氯酸盐(Th(.*)C1O(4)(-))与环己烯加成得到双加成产物，即反式-1，2-二(5-硫代菲)环己烷二高氯酸酯(1)，与其他烯烃和炔烃加成也得到反式双加合物，而与环辛烯加成只得到顺式一加成物，即1，2-(5，10-硫杂菲二基)环辛烷二氯酸酯(2a)。Th.+BF4-和Th.+Pf6-和Th.+Pf6-加成环辛烯得到类似的单加合物2b-d。根据单加合物的H-1和C-13核磁共振谱，根据其形成的化学计量比，以及它与NaSPh反应的化学计量比，推断了单加合物的结构，得到了等摩尔环辛烯、硫杂菲和二苯二硫化物。用X-射线单晶衍射法对其结构进行了确认。将Th.+盐加到环戊烯和环庚烯中，得到单加合物和双加合物的混合物。用X-射线单晶衍射法从少量单加合物中分离出Th.+SbF6-与环戊烯的双加合物，证明其具有反式构型。
Whereas the addition of thianthrene cation radical perchlorate (Th(.*)C1O(4)(-)) to cyclohexene gives a bisadduct, namely, trans-1,2-bis(5-thianthreniumyl)cyclohexane diperchlorate (1), and additon to other alkenes and alkynes also gives trans-bisadducts, addition to cyclooctene gave only a cis-monoadduct, namely, 1,2-(5,10-thianthreniumdiyl)cyclooctane diperchlorate (2a). Similar monoadducts 2b-d were obtained from the adition of Th.+BF4-, and Th.+PF6-, and Th.+PF6- to cyclooctene. The structure of the monoadduct was deduced from its H-1 and C-13 NMR spectra, from the stoichiometry of its formation, and from the stoichiometry of its reaction with NaSPh, which gave equimolar amounts of cyclooctene, thianthrene, and diphenyl disulfide. The structure was confirmed with X-ray crystallography. Addition of Th.+ salts to cyclopentene and cycloheptene gave mixtures of mono- and bisadducts. The bisadduct of Th.+SbF6- to cyclopentene, separated from the small amount of monoadduct by crystallization, was shown with X-ray crystallography to have the trans configuration.