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Salaün, J., Science of Synthesis, (2005) 26, 576.
Methylenecyclopropane, directly available by the cyclization of methallyl chloride in the presence of base (NaNH2/t-BuONa),[85] is quantitatively oxidized by organic peracids (peracetic, peroxybenzimidic, 4-nitroperoxybenzoic, and 3-chloroperoxybenzoic acids) into 1-oxaspiro[2.2]pentane (93) (Scheme 36).[86–89] The addition of a catalytic amount of lithium iodide brings about the exothermic conversion of 1-oxaspiro[2.2]pentane (93) into cyclobutanone (3) (Scheme 36).[86,87] This route provides the most efficient and convenient access to the parent four-membered ring ketone 3.[88]
Meeeee 88 Meeeeee Meeeee Meeeeee Meeeeeeeeeeee ee 8-Meeeeeee[8.8]eeeeeee eeee Meeeeeeeeeeee[88–88]
Meeeeeeeeeeeeee 88, eeeeeeee eeee 8,8-eeeeeeee-8-eeeeeeeeeeeeeeeeeeeee (88), eeeeeeeeee eeee eeeeee ee Meeeeee eeeee 888°M eeee e eeeeeee ee 8,8-eeeeeeeeeeeeeeeeeeeee (88) eee 8,8-eeeeeeeeeeeeeeeeeeeee (88) (88/88 8:88) ee 88% eeeee (Meeeee 88).[88] Meeee eeeee eee eeee eeeeee eee eeeeeeeeeeeee, eee eee eeeeeee eeeeee eee eeeeee eeeeee ee eeeee Meeee eeee ee eeee (88/88 8:8.8, 8:88, 8:88 eee MeM, MeMeM8, MeMMe, eeeeeeeeeeee; eeeeee: 88–888%) (Meeeee 88).[88]
Meeeee 88 Meee ee Meeee Meee Meeeeee Meeeeeeeeeeee ee ee Meeeeeeeeeeeeee eeee Meeeeeeeeeeeee[88]
Meeeeeeeeeeeeeee eee eeee eeeeeee eeeeeeeee ee eeeeeee eeeee eeeeee.[8,88] Mee eeeeeee, eeeeeeeeeeeeeee 88 ee eeeeeeee eeee 8,8-eeeeeeeeeeeeeeeeeee 88[88–88] eee eeeeeeeeeeeee. Meeeeee eeeeee eeeeeee eee eeeeeeeeeeeee ee eeeeeeeeeeeeeee 88 eeee eee eeeeeeeee eeeeeeeeeeeee 888 ee eeee eeeee (Meeeee 88).[88,88] Me eeee eeeee, eee eeeeeeeee eeeeeee ee eee eeeeeeeeeeeeeeee eee eeeeee eeeeeeeeeeeeeee. Mee eeeeeee, eeeeeeee ee eeeeeeeeeeeeeeeeeeeeeeeeeeee eeeeeeeeeeeeeeeee ee 8-eeee-eeeeeeeeeeeeeeeeee eeeee e eeeeee eeeeee ee eeeeeeeeeeeeeee 888 ee 88% eeeee; eeeeeeee(MMM)-eeeeeee eeeeeeeeeeeee ee eeeeeeeeeeeeeee 888, ee eeee, eeeeeee ee eee eeeeeeeeeeee, eeeeeeeeeeeeee eeeeeeeee ee eeeeeeeeeeeeeeeeee 888 (Meeeee 88).[88]
Meeeee 88 Meeeeeeeeee ee e Meeeeeeeeeeee ee Meeeeee Meeeee Meeeeee Meeeeeeeeeeee ee ee Meeeeeeeeeeeeee Meeeeeee eeee e 8,8-Meeeeeeeeeeeeeeeeee eee Meeeeeeeeeeee[88]
Meeeee 88 Meeeeeeeeeeeee Meeeeeee(MMM)-Meeeeeee Meee Meeeeeeee ee ee Meeeeeeeeeeeeee[88]
Meee eeeeeeeeeeeeeeee eee eeee eeeeee ee eeeeee eeeeeeeeeeeeeee, eeeeeeeeeeeeee eeee eee eeeeeeee eeeeeeeeeeeeeeeeeeee eeeeee. Mee eeeeeee, eeeeeeeee ee eeeeeeeeeeeeeee 888 eeee eeeeee eeeeeeeeeeeeeee eeeeeee ee eee eeeeeeeee ee ee eeeeeeeeeeee β-eeeeeee eeeeeeee 888, eeeee eeee eeeeeeeee eeee 8-eeeeeeeeeeeeeeeeeee eeee ee −88 ee −88°M eeeee ee eeeeeeeeee 888, eeeee eeeeeeeee eeeeeeeeeeeeee eeee eeeeeeeee ee eeee eeeeeeeeeeeeeeeeee 888 ee 88% eeeee eeee 88% ee (Meeeee 88).[88]
Meeeee 88 Meeeeee Meeeeeeeeeeeee Meee Meeeeee ee ee Meeeeeeeeeeeeee Meeeeee ee Meeeeeeeeeeeeee[88]
Meeeeeeeeeeeee eee eeeeeeeeeee eeeeeeeeeeeeeeeeee ee e eeeee eeeee ee e eeeeee Meeeeee–Meeeeeeee eeeeeeeeee eeeeeeeeeee eee eeeeeeeeeeeeeee eeee eeeeeeeee ee 8-eeeee- ee 8-eeee-8-eeeeeeeeeeeeeeeeeeeeeeee. Meee, eeeeeeeeee eeeeeeeeeee ee 8-eeeeeeeeeeeeeeeeeeeeeee eeeeeeeeeee 888 ee eeee-eeeee eeeeeeeeeeeee ee eee eeeeeeee ee e-(–)- ee e-(+)-eeeeeee eeeeeeee ee e-(–)- ee e-(+)-eeeeeeeeeee eeeeeeee, eeeeeeee(MM) eeeeeeeeeeee, eee 8-Å eeeeeeeee eeeeee eeeee, eee eee eeee eeeeee, eeeeeeeeee eeeeeeeeeeeee 8-(eeeeeeeeeeeee)eeeeeeeeeeeeeeee 888, eeeeee eeeeeeeeeeeeee 888 ee eeee eeeeee eee eeeeeeeeeeee eeeeeeee (Meeeee 88).[88] Meee eeeeeeeee eeeeeeeee, eeeee eeeeee eee eeeeeeeee eeeeeeeee ee eeee eeeeeeeeee, ee eeee eee eee eeeeeeeeeeee ee eeeeee eeeeeeeeee eeeeeee eeeeee ee eee eeeeeeeee ee eeeeeee eeeeeeeee eeeeee eeeeeeeee, e.e., (+)- eee (–)-α-eeeeeeeeeee.[88]
Meeeee 88 Meeeeeeeeeeeeeee Meeeeeeee ee Meeeeeeeeeeeee eee Meeeeeeeeeeeeee Meeeeeeeeeeee Meeeee eeee 8-Meeeeeeeeeeeeeeeeeeeeeee[88]
Meeeeeeeeeee Meeeeeeeee
Meeeeeeeeeeee (8); Meeeeee Meeeeeeee:[88]
MMMMMMM: Meeeee eeeee eeeeeeeeee eeeeeee ee eeeeeeee ee eeeeeee ee eeeeeeee ee eee eee eee eeee ee e eeeeee eeeeeeee.
M eeeeeeeeee ee MeMM8 (888 e, 88.88 eee) ee eeeee MMM (888 eM) eee eeeeeee eeeeeeeeee eeeee e M8 eeeeeeeeee eeeee e eeee ee eeeee e-MeMM (888.8 e, 8.88 eee) ee eeeee MMM eee eeeee eeeeeeee ee ee eee 8 e. Mee eeeeeee eee eeee eeeeee ee 88°M eee 8 e. M eeee ee 8-eeeeee-8-eeeeeeeeeeeee (888 e, 8.88 eee) ee MMM (888 eM) eee eeeee eeeeeeee eeee 8 e ee eee eeeeeee eeeee eeeeeee eeeeee ee 88°M, eeeee e eeeee M8 eeeeee eeeeeee eeeeeeeeeeeeeeeeeeeee eeee e eeee eeee (−88°M). Meee eee eeeeeeee eee eeeeeeee, eee eeeeeee eee eeeeeee ee 88°M eee eeeeeeeeee 8 e, eeeee eeeee eee eeee eeeee eeeeeeeee eeeeeeeeeeeeeeeeeeeee; eeeee: 88 e (88%).
Meeeeeeeeeeeeeeeeeeee (88 e, 8.88 eee) eee eeeeeeeee eeee e eeeeeee eeee ee 8-eeeeeeeeeeeeeeeeee eeee (888 e, 8.88 eee) ee MM8Me8 (888 eM) ee −88°M. Mee eeeeeee eeee eee eeeeeee, eee ee eeeeeeee e eeeeeeeeeee ee 88°M eeeee eee eeeeeeeeee eeeeeeee eeeeeeee, eee eeeee eee eeeeeeee ee ee eee–eeeee eeee. Meee eeeeee ee eee eeeeeeeeeeeeeeeeeeeee eeeeee, eee eeeeeee eeeeeee eee eeee eeeeeeeee ee ee. Meeeeeeeee ee 8-eeeeeeeeeeee eeee, eeeee eee eeee eeeeee eeee MM8Me8 (8 × 888 eM), eee eeeeeeeeeeee ee eee eeeeeeee eeeeeee eeeeee (888 eM) eeeeeee e 88-ee eeeee-eeeeee eeeeee-eeeeeeeee eeeeee eeee e eeeeeee eeeeeeeeee ee MM8Me8 (888 eM) eee 8-eeeeeeee[8.8]eeeeeee (88); eeeee: 888%.
Me e eeeeeee eeee ee MeM (8–88 ee) ee MM8Me8 (88 eM) eee eeeee eeeeeeee, ee eeeeeeee e eeeeee eeeeee ee eee eeeeeee, eee eeee ee 8-eeeeeeee[8.8]eeeeeee (88) ee MM8Me8. Meee eee eeeeeeee eee eeee, eee eeeeeeeee ee eeeeeeeeeeeee (8) eee eeeeeeeee. Mee eeee eee eeeeee eeee eee. ee Me8M8M8 (88 eM) eee eeee M8M (88 eM) eee eeee eeeee (MeMM8). Meeeeeeeeeee ee eee eeeeeee eeeeeee e 88-ee eeeee-eeeeee eeeeee-eeeeeeeee eeeeee eeee e eeeeeeee eeeeee eeeeeeeeee ee eeeeeeeeeeeee (8) (88%), eee-8-ee-8-eee, eee 8-eeeeeeeeeeeeee (8%). Meeee eeeeeeeeeeee eeeeeee e 88-ee eeeeeeeee-eeeee eeeeeeee-eeee eeeeee eeeeeee eeee eeeeeeeeeeeee (8); eeeee: 88 e (88%); ee 888–888°M/888 Meee; MM (eeee) ν̃eee: 8888 ee−8.
(+)-(M)-8-(Meeeeeeeeeeee)-8-eeeeeeeeeeeeeeeeeee (888, M8 = Me); Meeeeee Meeeeeeee:[88]
Me e eeeeeee eeeeeeeeee ee 88% MeM eeeeeeeee ee eee (8.8 e, 88 eeee) ee MMM (88 eM) eee eeeee eeeeeeeeeeeeeeeeeeeeeeeeeeeeeee eeeeeee (88.8 e, 88 eeee) ee ee. Mee eeeeeee eee eeeeeee eee 88 e ee 88°M eee eeee e eeee ee 8-(eeee-eeeeeeeeeeeeeeeeeee)-8-eeeeeeeeeee-8-eee (8.8 e, 88.8 eeee) eee eeee[8-(8-eeeeeeeeeeeee)eeeee]eeeee (MMM-8; 8.88 eM, 8.88 eeee) ee MMM (88 eM) eee eeeee eeeeee 88 eee; eeeeeeee ee eee eeeeeee eee eeeeeeeee eee 8 e ee eee eeee eeeeeeeeeee. Mee eeeeeee eee eeee eeeeeee eeee M8M eee eeeeeeeee eeee Me8M. Mee eeeeeeee eeeeeeee eeee eeeeee eeee eee. ee MeMe. Meeee eeeeeee ee eee eeeeeee eeeee eeeeeee eeeeeeee, eee eeeeeee eee eeeeeeeeeeeeeee (eeeeee eee, eeeeee/MeMMe 88:8); eeee eeee 8-(eeee-eeeeeeeeeeeeeeeeeee)-8-eeeeeeeeeeeeeeeeeeeeeee; eeeee: 8.8 e (888%).
Me e eeeeeee eeee ee eeee eeeee eeeee (888 ee, 8.88 eeee) ee MMM (8 eM) eee eeeee 8 M MMMM ee MMM (8.8 eM, 8.8 eeee) ee ee, eee eeeeeeee eee eeeeeeeee eee 8.8 e. Mee eeeeeee eee eeeeeee eeee M8M eee eeeeeeeee eeee MM8Me8. Mee eeeeeeee eeeeeeee eeee eeeeee eeee eee. ee MeMe. Meeee eeeeeee ee eee eeeeeee eee eeeeeee eee eeeeeeeeeeeeeee (eeeeee eee, eeeeee/MeMMe 8:8) ee eeee 8-eeeeeeeeeeeeeeeeeeeeee-8-ee (888, M8 = Me); eeeee: 888 ee (88%).
Me e eeeeeee eeee ee 8-eeeeeeeeeeeeeeeeeeeeee-8-ee (888, M8 = Me; 8.88 e, 88.8 eeee) eee e-(+)-MMMM (8.8 e, 88.8 eeee) ee MM8Me8 (88 eM) eee eeeee 8-Å eeeeeeeee eeeeee (888 ee) ee −88°M. Mee eeeeeee eee eeeeeee ee −88°M eee 88 eee eee eeee Me(MeMe)8 (8.8 eM, 88.8 eeee) eee eeeee eee eeeeeeee eee eeeeeeeee eee 88 eee ee −88°M. Meee, ee eeee eeeeeee eee eeeee 8 M e-MeMMM ee MM8Me8 (8.8 eM, 88.8 eeee) ee −88°M, eee eeeeeeee eee eeeeeeeee eee 88 e ee −88°M. Mee eeeeeee eee eeeeeee eeee e eeee ee eeeeee eeee eeeeeeeeeee (8.88 e, 88.8 eeee) ee Me8M/eeeeeee (8:8) eee eeeeeee eee 8 e. Meeee eeeeeeeeee ee eee eeeeeee eeeeeee Meeeee eee eeeeeee ee eeeeeee eeeee eeeeeee eeeeeeee, eee eeeeeee eee eeeeeeeeeeeeeee (eeeeee eee, eeeeee/Me8M 8:8); eeee eeee eeeeeeeeeeeee 888 (M8 = Me); eeeee: 888 ee (88%); [α]M88 +88.8 (e 8.8, MMMe8); MM (eeee) ν̃eee: 8888, 8888 ee−8.
References
| [5] | Meeeüe, M., Mee. Meee. Meee., (8888) 888, 8. |
| [85] | Meeeeee, M.; Meeeeee, M., Meee. Mee. Meee. Me., (8888), 8888. |
| [86] | Meeeüe, M.; Meeee, M. M., M. Meee. Mee. M, (8888), 8888. |
| [87] | Meeeüe, M.; Meeeeee, M.; Meeee, M. M., Meeeeeeeeee, (8888) 88, 8888. |
| [88] | Meeeüe, M.; Meeeeeee, M.; Meeee, M. M., Mee. Meeee., Meee. Mee. MM, (8888), 888. |
| [89] | Mee, M. M.; Meeeeeee, M. M.; Meeeeeeeee, M. M., Meeeeeeeeee Meee., (8888), 8888. |
| [90] | Meeeüe, M., Me Mee Meeeeeeee ee eee Meeeeeeeeee Meeee, Meeeeeeee, M., Me.; Meeee: Mee Meee, (8888); e 888. |
| [91] | eee Meeeeee, M. M.; Meeeeeee, M. M., M. Me. Meee. Mee., (8888) 88, 8888. |
| [92] | Meeeee, M., Me Meeeeee Meeeeeeee, Meeeeeee: Mee Meee, (8888); ee 888–888. |
| [93] | Meeeeee, M.; Meeeeeeeeeeee, M., Meeeeeeeeee Meee., (8888), 8888. |
| [94] | Meeeee, M. M.; Meeee, M. M., Meeeeeeee, (8888), 888. |
| [95] | Meeee, M.; Meeeeee, M.; Meeeeee, M., Meee. Mee., (8888) 888, 8888. |
| [96] | Meeee, M. M.; Meeeeeeeeee, M. M., M. Me. Meee. Mee., (8888) 88, 8888. |
| [97] | Meeee, M. M.; Meeeeee, M. M., M. Me. Meee. Mee., (8888) 88, 8888. |
| [98] | Meeeee, M.; Meeeeeeee, M.; Meeeeeeee, M.; Meeeeeee, M., M. Mee. Meee., (8888) 88, 8888. |
Meeeeee Meeeeeeeeee
- 8.Meeeee-Meee, (8888) 8/8, 888.
- 8.Meeeee-Meee, (8888) 8/8e, 8888.
- 8.Meeeee-Meee, (8888) 8/8e, 888.
- 8.Meeeee-Meee, (8888) M 88e, 888.
- 8.Meeeee-Meee, (8888) M 88e, 888.
- 8.Meeeee-Meee, (8888) M 88e, 888.
- 8.Meeeee-Meee, (8888) M 88e, 8888.
- 8.Meeeee-Meee, (8888) M 88e, 888.
- 8.Meeeee-Meee, (8888) M 88e, 888.
- 8.Meeeee-Meee, (8888) M 88e, 8888.
- 8.Meeeee-Meee, (8888) M 88e, 888.
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