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Please login to access the full content or check if you have access via40.1.1.5.6.2.7.8 Variation 8: Dirhodium(II) Caprolactamate Catalyzed Oxidative Coupling of Tertiary Amines and Siloxyfurans
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Ipaktschi, J.; Saidi, M. R., Science of Synthesis Knowledge Updates, (2012) 4, 427.
Very similar to the copper-catalyzed cross-dehydrogenative coupling reaction of tertiary amines with siloxyfurans (Section 40.1.1.5.6.2.7.7), the oxidative coupling occurs also when rhodium is used as catalyst.[88] By heating a solution of N,N-dimethylaniline (116, Ar1 = Ph; R1 = H; R2 = Me; 2.0 equiv), 2-(triisopropylsiloxy)furan (117, R3 = H; 1.0 equiv), and dirhodium(II) caprolactamate (118; 1.0 mol%) in methanol at 60 °C in the presence of 1.2 equivalents of T-HYDRO (70% aq t-BuOOH), γ-(aminoalkyl)butenolide 119 (Ar1 = Ph; R1 = R3 = H; R2 = Me) is isolated in 95% yield (Table 19, entry 1). The catalyst loading can be reduced to 0.1 mol%, although a longer reaction time is then necessary. A selection of cross-dehydrogenative coupling reactions of tertiary amines 116 with siloxyfurans 117 catalyzed by dirhodium(II) caprolactamate (118) is depicted in Table 19. Noteworthy examples include an amine containing a vinyl group (Table 19, entry 7), an unsymmetrical N-ethyl-N-methylaniline which reacts selectively on the N-methyl group (entry 10), and a reaction with a substituted 2-siloxyfuran 117 (R3 = CH2CHCH2; entry 11).[88]
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Meeee | Me8 | M8 | M8 | M8 | Meeeee (%) | Mee |
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8 | Me | M | Me | M | 88 | [88] |
8 | 8-Mee | M | Me | M | 88 | [88] |
8 | 8-MeM8M8 | M | Me | M | 88 | [88] |
8 | 8-e-MeM8M8 | M | Me | M | 88 | [88] |
8 | 8-MMMM8M8 | M | Me | M | 88 | [88] |
8 | M | Me | M | 88e | [88] | |
8 | 8-M8MMMM8M8 | M | Me | M | 88 | [88] |
8 | Me | (MM8)8 | M | 88e | [88] | |
8 | Me | M | 88e | [88] | ||
88 | Me | M | Me | M | 88 | [88] |
88 | Me | M | Me | MM8MMMM8 | 88 | [88] |
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References
[88] | Meeeee, M. M.; Meeeeee, M. M.; Meeeeee, M. M.; Meeee, M. M., M. Me. Meee. Mee., (8888) 888, 8888. |