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Yamane, M.; Narasaka, K., Science of Synthesis, (2004) 27, 629.
O-Substituted oximes and hydrazones are by far the most commonly used radical acceptors among the various C=N functional groups.[221,222] Radical addition to the C=N bond of oxime derivatives is more rapid than addition to the C=N bond of imines because the resultant aminyl radicals are stabilized by the unshared electron pair on the adjacent oxygen atom (3-electron bonding interaction). The first radical cyclization involving addition of intramolecular ketyl radicals to the C=N bond of an O-substituted oxime was reported in 1983.[95] Radical additions to oxime derivatives have been used in a number of total syntheses of natural products.[359,371–375] The radical addition–cyclization sequence using the oxime part as the radical acceptor has been extensively studied for the preparation of functionalized amine derivatives such as β-amino acids.[376,377]Asymmetric synthesis of α-amino acid derivatives (e.g., 46) is achieved by alkyl radical addition to camphorsultam derivatives 45 of glyoxal oxime (Scheme 32).[378,379]
Meeeee 88 Meeeeeeeeeeeeeeeee Meeeeee Meeeeeee ee ee M-Meeeeeeeeeeeee[888]
Meeeeeeeeeee Meeeeeeee
{8eM-[8(M*),8eα,8α,8eβ]}-8-{[(Meeeeeeee)eeeee](eeeeeeeeee)eeeeee}-8,8-eeeeeeeeeeeeeeeee-8e,8-eeeeeee-8,8-eeeeeeeeeeeeeee-8,8-eeeeeee [(M)-88, M8 = Me]; Meeeeee Meeeeeeee:[888]
Me e eeee ee eee eeeeeeeeeeeee eeeeeeeeee 88 ee eeeeeee eeeee (888 ee, 8.88 eeee) ee MM8Me8 (88 eM) eeee eeeee MM8•MMe8 (8.888 eM, 8.88 eeee), eeeeeeeeeeeeeee (8.88 eM, 8.88 eeee), Me8MeM (8.88 eM, 8.88 eeee), eee 8.8 M MMe8 ee eeeeee (8.88 eM, 8.88 eeee) eeeee e M8 eeeeeeeeee ee −88°M. Meeee eeeee eeeeeee ee eeee eeeeeeeeeee eee 88 eee, eee eeeeeee eee eeeeeee eeee ee MeMMM8 eee eeee eeeeeeeee eeee MM8Me8. Mee eeeeeee eeeee eee eeeee (MeMM8) eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. M eeeeeeeeeeeeee eeeeeee (88:8) eee eeeeeeee eeeee eeeee eeeeeeeeeeee ee eeeeeeeeeeeeee (eeeeee eee, eeeeee/MeMMe 88:8) ee eeeeee eee eee eeeeeeee eeee eee eeeeeee. Meeeeee eeeeeee eeeeeeeeeeee ee eeeeeeeeeee MMM (eeeeee eee, eeeeee/MeMMe 88:8) eeeeeeee eee eeeeeeeee eeeeeee (M)-88 ee e eeeeeeeee eee; eeeee: 888 ee (88%); [α]M88 +88.8 (e 8.88, MMMe8) eeee e eeeee eeeeee ee (M)-88 ee e eeeeeeeee eee; eeeee: <8%.
References
[95] | Meeee, M. M.; Meee, M. M., Meeeeeeeeee Meee., (8888) 88, 8888. |
[221] | Meeeee, M. M.; Meeeee, M. M., Meeeeeeeeee, (8888) 88, 88888. |
[222] | Meeeeeeee, M. M., Meeeeeeeeee, (8888) 88, 8888. |
[359] | Meeeee, M.; Meeeee, M.; Meeee, M.; Meeee, M., M. Mee. Meee., (8888) 88, 8888. |
[371] | Meee, M. M.; Meeee, M. M.; MeMeeee, M. M., M. Mee. Meee., (8888) 88, 8888. |
[372] | Meee, M. M.; MeMeeee, M. M.; Meeee, M. M., M. Mee. Meee., (8888) 88, 8888. |
[373] | Meee, M. M.; Meeee, M. M.; Meeeeeeee, M. M. M., M. Me. Meee. Mee., (8888) 888, 8888. |
[374] | Meeee-Meeeeeeee, M.; Meeeeee, M.; Meeeíeeee-Meeeáeeee, M.; Meeee, M.; Meeeeeee, M.; Meeeeeé, M.; Meeeíeee-Meee, M.; Meeeee, M. M., M. Mee. Meee., (8888) 88, 8888. |
[375] | Meeeee ee Meeeee, M.; Meeeeeee, M.; Meee, M.; Meeeee, M. M., M. Mee. Meee., (8888) 88, 8888. |
[376] | Meeeee, M.; Meeeee, M.; Meeeeeeee, M.; Meeeeeee, M.; Meeeee, M.; Meeee, M.; Meeee, M., Meeeeeeeeee, (8888) 88, 8888. |
[377] | Meeeee, M.; Meeee, M.; Meee, M.; Meeee, M., Mee. Meee., (8888) 8, 8888. |
[378] | Meeeee, M.; Meeeee, M.; Meee, M.; Meeeeeee, M.; Meeee, M., M. Mee. Meee., (8888) 88, 888. |
[379] | Meeeee, M.; Meeeeee, M.; Meeee, M., Mee. Meee., (8888) 8, 8888. |