Silver-Catalyzed 1,3-Aza-Benzyl Migration of Allyl Alcohol

Abstract

Carbon migration of alkenyl alcohols has been recognized as an increasingly viable methodology in organic synthesis. Herein, we disclose a silver-catalyzed 1,3-aza-benzyl migration of allyl alcohols by utilizing chelation-assisted selective cleavage of an unstrained C(sp3)–C(sp3) bond. This approach provides an available, efficient, high atom-economic, and environmentally benign procedure, leading to alkylation products with broad substrate scopes and excellent yields. The migration proceeds via a one-pot, two-step process involving a free-state alkyl metal species.

Copper-Catalyzed Aza-Benzyl Transfer Michael Addition via C–C Bond Cleavage

“…1 H NMR (600 MHz, CDCl 3 ) 8.49 (s, 1H), 7.69 (d, J = 8.4 Hz, 2H), 7.57−7.46 (m, 3H), 7.09 (d, J = 7.8 Hz, 2H), 7.07−6.98 (m, 4H), 3.90−3.79 (m, 1H), 3.35−3.24 (m, 2H), 3.19−3.11 (m, 2H), 2.26 (s, 3H). 13 C{ 1 H} NMR (151 MHz, CDCl 3 ) δ 197.9, 160.0, 149.3, 140.9, 136.3, 136.1, 136.0, 131.9, 129.8, 129.3, 128.1, 127.5, 123.9, 121.5, 45.3, 44.5, 41.5, 21.1.…”

“…1 H NMR (600 MHz, CDCl 3 ) δ 8.50 (d, J = 4.2 Hz, 1H), 7.52−7.49 (m, 1H), 7.45 (d, J = 7.8 Hz, 1H), 7.29 (t, J = 7.2 Hz, 1H), 7.18 (t, J = 7.2 Hz, 1H), 7.14 (d, J = 7.5 Hz, 1H), 7.10−6.06 (m, 6H), 3.84−3.74 (m, 1H), 3.31−3.20 (m, 2H), 3.08−3.17 (m, 2H), 2.27 (s, 3H), 2.20 (s, 3H). 13…”

“…■ EXPERIMENTAL SECTION General Information. 1 H and 13 C NMR spectra were recorded respectively on a Bruker 14A04336 (600 MHz) spectrometer and a Bruker 14A04336 (400 MHz) spectrometer. Chemical shifts were reported in parts per million (ppm), and the residual solvent peak was used as an internal reference: proton (chloroform δ 7.26), carbon (chloroform δ 77.0), or tetramethylsilane (TMS δ 0.00).…”

“…J = 7.8 Hz, 1H), 3.96−3.88 (m, 1H), 3.37 (d, J = 6.6 Hz, 2H), 3.20 (dd, J = 13.2 Hz, 7.8 Hz, 1H), 3.11 (dd, J = 13.2 Hz, 7.2 Hz, 1H) 13. C{ 1 H} NMR (101 MHz, CDCl 3 ) δ 198.3, 159.5, 149.4, 146.4, 137.1, 136.4, 134.3, 133.2, 129.8, 128.7, 128.2, 127.8, 126.8, 126.1, 123.8, 121.6, 45.0, 44.2, 41.4.…”

“…13 C{ 1 H} NMR ((151 MHz, CDCl 3 ) δ 198.4, 160.2, 147.9, 141.4, 137.1, 136.4, 134.1, 133.0, 130.0, 129.4, 129.1, 128.6, 128.3, 128.2, 127.7, 127.6, 127.1, 127.0, 126.0, 121.9, 44.3, 42.8, 37.7. HRMS (ESI): C 25 H 21 ClNO [M + H] + calculated 386.1306, found 386.1305.…”