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Volumn 49, Issue 40, 2010, Pages 7304-7307

Direct alkynylation of thiophenes: Cooperative activation of TIPS-EBX with gold and Brønsted acids

Author keywords

Alkynes; Cooperative catalysis; Direct alkynylation; Heterocycles; Hypervalent iodine

Indexed keywords

ALKYNES; ALKYNYLATIONS; COOPERATIVE CATALYSIS; HETEROCYCLES; HYPERVALENT IODINE;

EID: 77957334631     PISSN: 14337851     EISSN: 15213773     Source Type: Journal    
DOI: 10.1002/anie.201003179     Document Type: Article
Times cited : (193)

References (65)
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    • The effect of the Brønsted acid described here is different from the reported acceleration of a proto-deauration step; see: A. S. K. Hashmi, Catal. Today 2007, 122, 211.
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    • See the Supporting Information
    • See the Supporting Information.
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    • The success of TIPS-EBX 1 is probably caused by steric shielding, which prevents side reactions
    • The success of TIPS-EBX 1 is probably caused by steric shielding, which prevents side reactions.
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    • The synthesis of 1 proceeded in 79%yield over 2 steps from 2-iodobenzoic acid on a 30 g scale. This compound will soon be commercially available
    • V. V. Zhdankin, C. J. Kuehl, A. P. Krasutsky, J. T. Bolz, A. J. Simonsen, J. Org. Chem. 1996, 61, 6547. The synthesis of 1 proceeded in 79%yield over 2 steps from 2-iodobenzoic acid on a 30 g scale. This compound will soon be commercially available.
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    • For electron-rich thiophenes, the higher reactivity observed in presence of TFA is sometimes counterbalanced by the acidmediated decomposition. In some cases, better yields are obtained without TFA. The optimal conditions are given in Table 2.
    • For electron-rich thiophenes, the higher reactivity observed in presence of TFA is sometimes counterbalanced by the acidmediated decomposition. In some cases, better yields are obtained without TFA. The optimal conditions are given in Table 2.
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    • 2-Bromo-3-hexyl-, 2-formyl-and 3-acetyl-thiophenes were tested
    • 2-Bromo-3-hexyl-, 2-formyl-and 3-acetyl-thiophenes were tested.
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    • The low regioselectivity observed for benzothiophene could not yet be rationalized
    • The low regioselectivity observed for benzothiophene could not yet be rationalized.
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    • When the reaction was carried out in the presence of 3,5-di-tertbutyl-4- hydroxytoluol (BHT), full conversion was observed, but the reaction was impeded by the addition of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO). However, the result obtained with TEMPO could also be caused by the oxidative degradation of the catalyst
    • Angew. Chem. Int. Ed. 2010, 49, 3334. When the reaction was carried out in the presence of 3,5-di-tertbutyl-4-hydroxytoluol (BHT), full conversion was observed, but the reaction was impeded by the addition of 2,2,6,6- tetramethylpiperidine-1-oxyl (TEMPO). However, the result obtained with TEMPO could also be caused by the oxidative degradation of the catalyst.
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    • Lu, P.F.1    Boorman, T.C.2    Slawin, A.M.Z.3    Larrosa, I.4
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    • 3Cl] itself was a viable catalyst for the reaction, although less efficient than AuCl (see the Supporting Information)
    • F. Bonati, A. Burini, B. R. Pietroni, R. Galassi, Gazz. Chim. Ital. 1993, 123, 691. [AuPPh3Cl] itself was a viable catalyst for the reaction, although less efficient than AuCl (see the Supporting Information).
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    • The TfOH adduct of 1 is a well-behaved solid compound that could be fully characterized (see the Supporting Information). In contrast, the TFA adduct gave an oil upon evaporation of the solvent; further studies to determine its structure are under way
    • The TfOH adduct of 1 is a well-behaved solid compound that could be fully characterized (see the Supporting Information). In contrast, the TFA adduct gave an oil upon evaporation of the solvent; further studies to determine its structure are under way.
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    • 1,4-Bis(triisopropylsilyl)buta-1,3-diyne and 2-iodo benzoic acid were detected as the major products by 1H NMR spectroscopy and GC-MS, but could not be separated from other impurities formed during the reaction.
    • 1,4-Bis(triisopropylsilyl)buta-1,3-diyne and 2-iodo benzoic acid were detected as the major products by 1H NMR spectroscopy and GC-MS, but could not be separated from other impurities formed during the reaction.


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