2003
DOI: 10.1021/jo030173h
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Adducts of Phenoxathiin and Thianthrene Cation Radicals with Alkenes and Cycloalkenes

Abstract: Phenoxathiin cation radical perchlorate (PO.+ClO4(-)) added stereospecifically to cyclopentene, cyclohexene, cycloheptene, and 1,5-cyclooctadiene to give 1,2-bis(5-phenoxathiiniumyl)cycloalkane diperchlorates (4-7) in good yield. The diaxial configuration of the PO+ groups was confirmed with X-ray crystallography. Unlike additions of thianthrene cation radical perchlorate (Th.+ClO4(-)) to these cycloalkenes, no evidence for formation of monoadducts was found in the reactions of PO.+ClO4(-). This difference is … Show more

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Cited by 23 publications
(33 citation statements)
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“…Among these reactions, additions to alkenes and cycloalkenes, which were first discovered more than 20 years ago [15,16], have drawn, recently, further extensive interest [17][18][19][20]. Thus, whereas earlier [15][16][17] it was believed that addition of thianthrene cation radical perchlorate (Th •+ ClO − 4 ) to alkenes and cycloalkenes gave only bisadducts, it was found more recently that mono- (2) and bisadducts (3) are formed, in relative amounts depending on the structure of the alkene and cycloalkene [18][19][20]. Furthermore, it was found in these additions that the configuration of the alkene was retained in both types of adduct.…”
Section: Introductionmentioning
confidence: 99%
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“…Among these reactions, additions to alkenes and cycloalkenes, which were first discovered more than 20 years ago [15,16], have drawn, recently, further extensive interest [17][18][19][20]. Thus, whereas earlier [15][16][17] it was believed that addition of thianthrene cation radical perchlorate (Th •+ ClO − 4 ) to alkenes and cycloalkenes gave only bisadducts, it was found more recently that mono- (2) and bisadducts (3) are formed, in relative amounts depending on the structure of the alkene and cycloalkene [18][19][20]. Furthermore, it was found in these additions that the configuration of the alkene was retained in both types of adduct.…”
Section: Introductionmentioning
confidence: 99%
“…Furthermore, it was found in these additions that the configuration of the alkene was retained in both types of adduct. A mechanism of addition was formulated to explain these results [19,20] and is shown in scheme 1. The scheme shows that stereospecific cycloaddition of Th •+ to a double bond forms an intermediate, a cyclic distonic cation radical (1).…”
Section: Introductionmentioning
confidence: 99%
“…These data 11,12 have prompted us to look in the literature for aromatic groups that may also have an effect on cis and trans-vinylic protons opposite from that which is stated in the Tobey-Simon rule. We have collected data from the literature that are presented in Tables 1-5.…”
Section: Resultsmentioning
confidence: 99%
“…Recently, we have reported 1 H NMR data for five (E)-and 12 (Z)-5-thianthreniumylalkenes (4 and 5) 11 and of 14 (E)-and 11 (Z)-10-phenoxathiiniumylalkenes (6 and 7, Fig. 1).…”
Section: Introductionmentioning
confidence: 99%
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