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40.1.1.5.6.2.7.8 Variation 8: Dirhodium(II) Caprolactamate Catalyzed Oxidative Coupling of Tertiary Amines and Siloxyfurans

DOI: 10.1055/sos-SD-140-00123

Ipaktschi, J.; Saidi, M. R.Science of Synthesis Knowledge Updates, (20124427.

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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