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Synlett 2013; 24(1): 117-119
DOI: 10.1055/s-0032-1317859
DOI: 10.1055/s-0032-1317859
letter
Variations in Site of Lithiation of N-[2-(4-Methoxyphenyl)ethyl]pivalamide – Use in Ring Substitution
Further Information
Publication History
Received: 07 November 2012
Accepted after revision: 19 November 2012
Publication Date:
11 December 2012 (online)
Abstract
Lithiation of N-[2-(4-methoxyphenyl)ethyl]pivalamide at –20 to 0 °C with three equivalents of n-BuLi in anhydrous THF, followed by reactions with various electrophiles, gives high yields of products involving ring substitution ortho to the pivaloylaminoethyl group, which was unexpected in view of earlier results reported with t-BuLi.
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References and Notes
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- 14 Analytical Data for 7 White solid (0.32 g, 92%); mp 179–181 °C. FTIR: νmax = 3321, 2958, 1627, 1575, 1292, 1243 cm–1. 1H NMR (500 MHz, CDCl3): δ = 7.35–7.26 (m, 11 H, OH and 2 C6H5), 7.16 (d, J = 8.3 Hz, 1 H, H-6 of 4-MeOC6H3), 6.79 (dd, J = 2.8, 8.3 Hz, 1 H, H-5 of 4-MeOC6H3), 6.24 (d, J = 2.8 Hz, 1 H, H-3 of 4-MeOC6H3), 6.15 (br, exch., 1 H, NH), 3.63 (s, 3 H, OCH3), 3.37 (app q, J = 7 Hz, 2 H, CH2 NH), 2.60 (t, J = 7.2 Hz, 2 H, CH2), 1.11 [s, 9 H, C(CH3)3] ppm. 13C NMR (125 MHz, CDCl3): δ = 178.8 (s, C=O), 156.9 (s, C-4 of 4-MeOC6H3), 147.1 (s, C-1 of 2 C6H5), 146.6 (s, C-2 of 4-MeOC6H3), 132.8 (d, C-6 of 4-MeOC6H3), 130.7 (s, C-1 of 4-MeOC6H3), 127.9 (d, C-3/C-5 of 2 C6H5), 127.7 (d, C-2/C-6 of 2 C6H5), 127.2 (d, C-4 of 2 C6H5), 117.1 (d, C-3 of 4-MeOC6H3), 111.9 (d, C-5 of 4-MeOC6H3), 83.0 (s, COH), 55.0 (q, OCH3), 41.1 (t, CH2NH), 38.4 [s, C(CH3)3], 32.5 (t, ArCH2), 27.5 [q, C(CH3)3] ppm. MS (EI): m/z (%) = 399 (77) [M – H2O]+, 298 (99), 285 (90), 261 (33), 239 (10), 222 (26), 209 (31), 193 (73), 165 (53), 152 (13), 105 (48), 83 (100). HRMS (EI): m/z calcd for C27H29NO2 [M – H2O]+: 399.2198; found: 399.2187.
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