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26844517620
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note
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Use of XPhos gave superior results as compared to tri-(o-tolyl)- phosphine, 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (BINAP), and 2-dicyclohexylphosphino-2′,6′-dimethoxy-1,1′-biphenyl (SPhos).
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26844543037
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note
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(b) XPhos is commercially available.
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26844538263
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note
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In the absence of palladium catalyst, none of the coupling products were observed.
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54
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26844554657
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note
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Best results were obtained by further drying commercially available anhydrous potassium phosphate (160 °C, 0.1 Torr, 12 h) and handling it under inert atmosphere.
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55
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0031021265
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For a discussion on the competitive elimination reaction to give ynoates in studies concerning the palladium-catalyzed C-O and C-S bond formation, see: Rossi, R.; Bellina, F.; Mannina, L. Tetrahedron 1997, 53, 1025-1044.
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note
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See Supporting Information for details.
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61
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0000418343
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For a discussion on the competitive loss of triflates via nucleophilic attack at the sulfur center during N-arylation of amines with electron-deficient aryl triflates, see: (a) Wolfe, J. P.; Buchwald, S. L. J. Org. Chem. 1997, 62, 1264-1267.
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26844493116
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note
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For a discussion on the rate of reductive elimination and C-N bond formation in N-arylation of azaheterocycles, see ref 2c.
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note
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The immediate heating of the starting reaction components to temperatures above 60 °C is not recommended. In the case of triflate 5a, omission of this incubation time resulted in a noticeable decrease in the efficiency of the coupling reaction.
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note
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n-palladium complexes due to higher concentration of the aza-anion may also be in part responsible for the observed lower reactivity of acidic azaheterocycles; see ref 2c.
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note
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The ease of stereospecific synthesis of fully substituted vinyl triflates as compared to the corresponding vinyl iodides is noteworthy; see refs 8-10.
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For the general procedure used to prepare the vinyl triflate 5a, see: Kim, H.-O.; Ogbu, C. O.; Nelson, S.; Kahn, M. Synlett 1998, 1059-1060.
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