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Alberti, M. N.; Tzirakis, M. D.; Orfanopoulos, M., Science of Synthesis, (2009) 38, 488.
Cycloheptatriene may be transformed into compound 68, which is then subjected to [4 + 2] addition of singlet dioxygen to form a separable mixture of peroxide diastereomers endo-69/exo-69 in a 6:1 ratio (Scheme 15).[64,65] The major isomer endo-69, after separation using flash chromatography (silica gel), is transformed into the fully oxygenated hexose, l-glucose.[64]
Meeeee 88 Meeeeeeeeeeeee ee e Meeeeeeeeeeeeee[88,88]
Meeeeeeeeeeeeeee eee ee e eeeeeee eeeeeeeee ee eeee ee eee eeeeee eeeeeeee ee eeee-eeeeee eee ee eeeeeee eeeeeee eeeeeeeeeeeee; eeeee eeeeeeeee eee eeeeeeeeeee ee Meeeee 88. Meeeeeeeeeeeeeeee eee eeeee ee eee eeeeeeeeeee eeeeee 88 ee eee eeeeeeeeeeee eeeeeee eeeeee 88. Mee eeeeee eeeeeeeeee-8,8,8-eeeeee 88/88 (M8 = M)[88] ee eeee ee e eeeeee ee 8-eeeeeeeeeee eeeeeeeeeeeeeeeee 88/88 (M8 = MM, MM8Me, MMM, MMe, Me, 8-MeM8M8, 8-MeMM8M8, Me, Me, eMe, e-Me),[88–88] eeee eeee eeeeeeeee ee eeeeeeeeeeeeeee eeeeeee eeeeeeeeeee. Me eee eeeee eeeeeeeeeee eeee eeeeeeeeeeeee 88 eee eeeeeeeeeeee eeee eeeeeeeeeeeee 88 eee eeeeeeee (Meeeee 88). Me eeeeeeeeee, eeeee eeeeeeeeee eeeeee eeeeeeeeeeeee eee ee eeeeeeeeee eeeeeeee ee eeeee eeeeeeeeeeeeee (eeeeee eee) eee/ee eeeeeeeeeeeeeeeee. Meee eee eeeeee ee eeeeeeee eeeeeeee, eee eeeeeeeeee eeeeee eee eee eeeeee eeeeee ee eee 8-eeeeeeeeeee ee eee eeee eeeeeeeee eeeeeeeeeee eee ee eeeeeeee.
Meeeee 88 Meeeeeeeeeeeee ee 8-Meeeeeeeeee Meeeeeeeee-8,8,8-eeeeeee[88–88]
M8 | Meeeeeeeee | Meeeee (%) | Mee | |
---|---|---|---|---|
88 | 88 | |||
M | MMe8, 8 °M | 88e | 8.8e | [88] |
MM | MMe8, 8 °M | e.e. | 88e | [88,88] |
MM8Me | MMe8, 8 °M | e.e. | 88e | [88] |
MMM | MMe8, 8 °M | e.e. | 88e | [88] |
MMe | MMe8, 8 °M | 88e | e.e. | [88] |
Me | MMe8, 8 °M | 8e | 88e | [88] |
8-MeM8M8 | MM8Me8, −88 °M | 8.8e | 88e | [88] |
Me | MM8Me8, −88 °M | 88e | 88e | [88] |
8-MeMM8M8 | MM8Me8, −88 °M | 88e | 88e | [88] |
Me | MM8Me8, −88 °M | 88e | 88e | [88] |
Me | MM8Me8, −88 °M | 88e | 88e | [88] |
eMe | MM8Me8, −88 °M | 88e | 88.8e | [88] |
e-Me | MM8Me8, −88 °M | 88e | 88e | [88] |
e e.e. = eee eeeeeeee.
e Meeeeeee eeeee eeeee eeeee eeeeeeeeeeeeee eee/ee eeeeeeeeeeeeeeeee.
e Meeeeeeeee ee 8M MMM eeeeeeeeeeee eeeee 8-eeeeeeeeeeeeeeeeee ee eeeeeeee eeeeeeee; e eeeeeee ee 8–8 eeeeeeeeeee eeeeeeeeeeeeee.
Meeeeee eeeeee [8 + 8] eeeeeeeeeeeee ee eee eeeee eee(eeeeeeeeeeeeeeee) 88 eeeeeeee eeeeeee eee eeeeeeeeeeee eeeeeee eeeeee eeeeeee ee e eeeeee, eeeeeeeee eee eeeeeeeeee eeeeee eeeeeeeeeeee 88.[88] Mee eeeeeeee ee e eeeeee eeeeeeeeee ee eeeeeee eeeeeeee ee eee eeeeeeeeeeeeeeee eeee ee 88 eeeee eee-eee(eeeeeeeeeeee) eee(eeeeeeeeeeee) 88 (Meeeee 88).[88]
Meeeee 88 Meeeeeeeeeeeee ee e Meeee Meeeeeeeeeeeeeee[88]
Meeee eee 8888e, eeeeeee (eeeeeeeeee-8,8,8-eeeee-8-eee) eee eeeeeeeee (8-eeeeeeeeeeeeeeeee-8,8,8-eeeee-8-eee) eeeeeeeeeee eeee eeeeeeeeee eeeeeee eeeeeeee. Meeee eeeeeeeeeee eeee eeeee eeeeeeeeeeee eeeeeeee eee ee eeeee eeeeeeeeee eeeeeeeeee. Me eeeeeeee, eee eeeeeee eee eeeeeeeee eeee eeeeeee eeeeeeeee eee eee eeeeeeeeee eeeeeee ee e eeee eeeee ee eeeeeee eeeeeeee.[88] Mee eeeeeeeeeee ee eeeeeee eee eeeeeeee eeeeeeeee eeeeee ee eeeee eeeeeeeee eeeeeeeee eeeeeee e eeeeeeeeeee eeeeeee.
Meeeeeeeeeeeee ee eeeee 8M-eeeeeeeeee[e]-8,8-eeeeeee-8-eeeeeeeeeee eeeee eee eeeeeeee eeeeeeeeeeee 88 ee 88% eeeee.[88] Meee eee eeeeeeeee ee eeeeeeeeeeee 88 ee eeeeeee eee eeee eeeeeeee ee eeeeeeee, eee eeeeeeeee 88 ee eeeeeeee ee 88% eeeee (Meeeee 88). Meeeeee, eeee eeeeeeee 88 ee eeeeeee eeee eeeeee eee, eee eeeeeeeee 88 ee eeeeeeee ee 88% eeeee. Mee eeeeeeeeeeeeee ee eeeeeeeeeeee eeeeeeeeeee 88 (M8 = M, MM8Me) eee eeee eeeeeeeee (Meeeee 88).[88] Me eeee eeeee, eee eeeeeeee eeeeeeeeeeeee 88 eee eeeeee ee eeee eeeeee. Meeeeeeeeeee, eee eeeeeeee ee eeeeeeeeeeee 88 (M = M) eeee eeeeeeee eeeeeee 8-eeeeeee-8M-eeeeeeeeeeeeeeee-8-eee ee eeeeeeeeeeee eeeee.[88]
Meeeee 88 Meeeeeeeeeeeee ee Meeeeeeeeeeeeeeee[88,88]
Meeeeeeeeeee Meeeeeeee
8-(eeee-Meeeeeeeeeeeeeeeeee)-8,8-eeeeeeeeeeee[8.8.8]eee-8-eee (88):[88]
Meeee eeeee 88 (88.8 e, 8.888 eee) eee eeeeeeeee ee MM8Me8 (888 eM) eee MeMM (888 eM), eee eeee-eeeeeeeeeeeeeeeeeeee (88 ee, 88 μeee) eee eeeee. Mee eeeeeee, eeeee eeeeeee ee 8 °M, eee eeeeeeeeee eeee e 888-M Me eeee (Meeeeee Meeeeeee, eeeee MM 888) eeeee M8 eee eeeeeee eeeeeee eee eeeeeee. Meee eee eeeeeeee eee eeeeee ee ee eeeeeeee eee eeeeeee eee eeeeeee eee eee eee eee eeeee eeeeeeeeeeeeeee (eeeeee eee, eeeeeeeee eeeee/MeMMe 88:8 ee 88:8). Meee eeeeeeee eeee eeee-88; eeeee: 88.8 e (88%).
8,8-Meeeeeeeeeee[8.8.8]eeee-8,8-eeeeee 88 eee 8,8-Meeeeeeeeeeee[8.8.8.88,8]eee-8-eeee 88; Meeeeee Meeeeeeee:[88,88]
M MMe8 (MMMMMMM: eeeee) (ee MM8Me8) eeee ee eee eeeeeeeeeeeeeeee 88/88 (8%) eee eeeeeeeeeeeeeeeeeeee eeeeeeeeee (8 ee eee 88 eM eeee) ee 8 °M (ee −88 °M) eee eeeeeeeeee eeee e 888-M (ee 888-M) Meeeeee Meeeeeee Me eeeeeeeeee eeeee eeeeeee e eeee eeeeee ee eee M8 eeeeeeeeeeee eeeeeee eee eeeeeee. Mee eeeeeeee ee eee eeeeeeeeeeeeee eee eeeeeeeee ee 8M MMM eeeee eeeeeeeeeee eeeeeeee eeeeeeeeeee ee eee eeeeeeee eeeeeeee eee eeeeeeee. Mee eeeeeee eee eeeeeeeeee (88 °M/88 Meee) eee eee eeeeeee eee eeeee eeeeeeeeeeeeeee ee 88 °M (eeeeee eee, MM8Me8/eeeeeee). Meeee eeeeeeeeeeee eee eeeeeeee ee eeeeeeeeeeeeeeeee ee eeeeeeeeee eeeeeeeeeeee. Me eee eeee ee eeeeee eeeeeeee, eeeeeeeeee eeeee eeeeeeeeeeeeee (eeeeee eee) eee eeeeeeeee eee eeeeeeeeee eee eeeeeee. Mee eeeeeee eee eeeeeeeeee ee Meeeee 88.
Meeeeeee 8,8e,8,8,8,8e-Meeeeeeee-8,8-eeeeeeeeeeeeeeeeee[8,8]eeeee[8,8]eeeeeeeeeeee-8,8-eeeeeeeeeeeee (88):[88]
Meeeeeeeeeeeeeeeeeee (88 ee, 88 μeee) eee eeeeeee 88 (888 ee, 8.88 eeee) eeee eeeeeeeee ee MMe8 (88 eM) (MMMMMMM: eeeee). Mee eeee eee eeeeeeeeee eeee e 88-M eeeeeeeeee eeee eeeee e eeee eeeeee ee eee M8 eee eeeeee eeeeeeeeeeee eeeeeee eee eeeeeee ee 88 °M. Meeee e eeeee eeeeeeeeeee eeee ee 8 e, eee eeeeeee eee eeeeeeeeee ee 8–88 °M. Mee eeeeeee eee eeeeeeee [Meeeeeee (8 e), MMMe8 (888 eM)] ee eeee eeeeeeeeeeee 88 ee e eeeeeeeee eeeee; eeeee: 88 ee (88%); ee 888–888 °M.
Meeeeeee 8,8e,8,8,8e,8,8e,8,8,8e-Meeeeeeee-8,8:8,8-eeeeeeeeeeeeeeeeeeeeee[e,e]eeeeeeeeeee-8,8-eeeeeeeeeeeee (88):[88]
Mee(eeeeeeeeeeee) eee-88 eee eeeeeeeeeee ee e eeeeeee eeeeee ee 88 eeeee. Meee, eeeeeeeeeeeeeeeeeeee (88 ee, 88 μeee) eee eeeeeeeeeeee 88 (888 ee, 8.88 eeee) eeee eeeeeeeee ee MMe8 (88 eM) (MMMMMMM: eeeee). Mee eeeeeeee eee eeeeeeeeee eeee e 88-M eeeeeeeeee eeee eeeee e eeee eeeeee ee eee M8 eee eeeeee eeeeeee ee eeeeeeeeeeee ee 8 °M. Meeee e eeeee eeeeeeeeeee eeee ee 88 e, eee eeeeeee eee eeeeeeeeee ee 8–88 °M. Meee, eeeeeeeeeeeeeee (MM8Me8/Me8M) ee eee eeeeeee eeeeeee eee(eeeeeeeeeeee) eee(eeeeeeeeeeee) eee-88 ee e eeeeeeeee eeeeee; eeeee: 88 ee (88%, ee eeeeeeee); ee 888–888 °M (eee).
Meeee 8,8-Meeeeee-8e,8-eeeeeeee-8eM-eeeeeeeeee[e]-8,8-eeeeeee-8-eeeeeeeeeee (88); Meeeeee Meeeeeeee:[88]
Meeee 8M-eeeeeeeeee[e]-8,8-eeeeeee-8-eeeeeeeeeee (888 ee, 8.88 eeee) eee eeeeeeeeeeeeeeeeeeee (88 ee, 88 μeee) eeee eeeeeeeee ee MMe8 (88 eM) (MMMMMMM: eeeee). Mee eeee eee eeee eeeeeeeeee eeee e 888-M eeeeeeeeee eeee, eeeee e eeee eeeeee ee eee M8 eee eeeeee eeeeeee eee eeeeeee ee ee. Meeee e eeeee eeeeeeeeeee eeee ee 88 eee, eee eeeeeee eee eeeeeeeeee (88–88 °M). 8M MMM eeeeeeee eeeeeeeee eeeeeeeeeeee eeeeeeeee ee eeeeeeeeeeee 88. Meeeeeeeeeeeeee (MM8Me8/Me8M) ee eee eeeeeee eeee eeee eeeeee eeeeeeee; eeeee: 888 ee (88%); ee 88–88 °M.
Meeee 8-Meeeeee-8-eeeeeeeeeeeee-8,8,8-eeeeee-8-eeeeeeeeeee (88):[88]
Meeeeeeeeeee 88 (888 ee, 8.88 eeee) eee eeeeeeeee ee MMMe8 (88 eM). M eeee ee eeeeeeee (88 ee, 8.88 eeee) ee MeMM (8 eM) eee eeee eeeee eeeeeeee eeee 88 eee. Meeee eee eeee eee eeeeeee ee ee eee 8 e, eee eeeeeee eee eeeee eeeeeeeeeeeeeee (eeeeee eee, MeMMe/eeeeee 8:8) ee eeee eeeeeeeee 88 ee eeee eeeeee eeeeeeee; eeeee: 88 ee (88%); ee 888 °M.
Meeee 8-Mee-8M-eeeeeeeeee[e]-8,8-eeeeeee-8-eeeeeeeeeee (88):[88]
M eeee ee eeeeeeeeeeee 88 (888 ee, 8.88 eeee) ee MMMe8 (88 eM) eee eeeeee eeee e eeeeee eee eeeeee (88 e) eeeeeeee eeee eeeeee, eee eee eeeeeeee ee eee eeeeee eee eeeeee eee 88 eee. Meeee e eeeee eeeeeee eeee ee 88 eee, eee eeeeeeee ee eee eeeeee eee eeeeee eee eeeeeee eee eeeeeeeee eeee MMMe8 ee eeee 88 ee eeee eeeeee eeeeeeee; eeeee: 888 ee (88%); ee 888 °M.
References
[64] | Meeeeee, M. M.; Meeeeeeeeee, M.; Meeeeeee, M. M., M. Me. Meee. Mee., (8888) 888, 8888. |
[65] | Meeeeee, M. M.; Meeeeeeeeee, M.; Meeeeeee, M. M.; Meeeeeeee, M. M., M. Mee. Meee., (8888) 88, 8888. |
[66] | Meee, M.; Meeee, M., M. Me. Meee. Mee., (8888) 888, 8888. |
[67] | Meee, M.; Meeee, M., M. Mee. Meee., (8888) 88, 8888. |
[68] | Meee, M.; Meeee, M.; Meeeeeee, M., M. Me. Meee. Mee., (8888) 888, 8888. |
[69] | Meee, M.; Meeeeee, M., Meeeeeeeeee Meee., (8888) 88, 8888. |
[70] | MeeeXM8;e͸M;ee, M.; Meeeee, M.; Meeee, ͸M;.; Meeeeee, M.; Meeee, M., M. Mee. Meee., (8888) 88, 8888. |
[71] | Meeeeee, M. M., Meee. M. Meee., (8888) 88, 8. |
[72] | Me͸M;eee, M.; MeeeXM8;e͸M;ee, M.; Meeee, M., Mee. M. Mee. Meee., (8888), 8888. |
[73] | Müeee, M.; Me͸M;eee, M.; Meeee, M., Meee. Meee. Meee, (8888) 88, 888. |