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Volumn 9, Issue 10, 2007, Pages 1907-1910

Synthesis of perfluoroalkylated benzenes and pyridines through cationic Rh(I)/modified BINAP-catalyzed chemo- and regioselective [2 + 2 + 2] cycloaddition

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EID: 34249283376     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol070456m     Document Type: Article
Times cited : (70)

References (64)
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    • For co-cyclotrimerization of perfluoroalkyleneynes with acetylene gas and (trimethylsilyl)acetylene, see ref 8
    • For co-cyclotrimerization of perfluoroalkyleneynes with acetylene gas and (trimethylsilyl)acetylene, see ref 8.
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    • A pentasubstituted benzene (shown below) was generated in a trace amount as a single regioisomer. Because cyclotrimerization of 8 is also sluggish under the present reaction conditions, formation of metallacyclopentadiene from two molecules of 8 may not be involved. Accordingly, the regioselective formation of this compound can be explained by the reaction of rhodacycle B with 8 instead of 2.equation presented
    • A pentasubstituted benzene (shown below) was generated in a trace amount as a single regioisomer. Because cyclotrimerization of 8 is also sluggish under the present reaction conditions, formation of metallacyclopentadiene from two molecules of 8 may not be involved. Accordingly, the regioselective formation of this compound can be explained by the reaction of rhodacycle B with 8 instead of 2.equation presented
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    • Ru catalysts are also effective for the [2 + 2 + 2] cycloaddition of 1,6-diynes with electron-deficient nitriles: (a) Yamamoto, Y.; Okuda, S.; Itoh, K. Chem. Commun. 2001, 1102.
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    • Yamamoto and co-workers recently demonstrated that the coordinating groups including halogens of nitriles play an important role in the Ru-catalyzed [2, 2, 2] cycloaddition of 1,6-diynes with nitriles: (a) Yamamoto, Y, Kinpara, K, Nishiyama, H, Itoh, K. Adv. Synth. Catal. 2005, 347, 1913
    • Yamamoto and co-workers recently demonstrated that the coordinating groups including halogens of nitriles play an important role in the Ru-catalyzed [2 + 2 + 2] cycloaddition of 1,6-diynes with nitriles: (a) Yamamoto, Y.; Kinpara, K.; Nishiyama, H.; Itoh, K. Adv. Synth. Catal. 2005, 347, 1913.
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    • In the present study, n-C6F13CCH (2) and n-C7F15CN (15) were used because of their commercial availability, their low toxicity, and their high solubility in (CH2Cl)2. The effect of alkyl chain length will be investigated in due course
    • 2. The effect of alkyl chain length will be investigated in due course.


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