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Chataigner, I.; Harrison-Marchand, A.; Maddaluno, J., Science of Synthesis, (2005) 26, 1178.
Several reviews have been devoted to the Dieckmann condensation.[94] Typically, this reaction consists of the cyclization of a dicarboxylic ester (or related function) to a 3-oxo ester under basic conditions (with bases such as alkaline alkoxides) and can thus be regarded as the intramolecular version of the Claisen condensation (see Section 26.10.2.1.2.2). Four-membered to large oxo-substituted rings can be accessed by this method, but cyclopentanones and cyclohexanones represent the core domain of its application. The 3-oxo ester pattern undergoes ready decarboxylation after cyclization, so the Dieckmann route is a useful source of cyclic ketones. Because the reaction is completely reversible, the retro-Dieckmann is a useful synthetic tool. The driving force of the condensation appears to be the ready deprotonation of the resulting 3-oxo ester, obtained in its enolate form in the basic medium. Kinetic and isotopic effects show that the rate-limiting step is the cyclizing addition of the primary enolate to the second ester. The competition between the inter- and intramolecular condensations explains why the Dieckmann reaction is often conducted under high-dilution conditions, especially when preparing medium to large ring ketones. The control of the regioselectivity represents one of the major difficulties associated with this reaction (this is also encountered in the Claisen condensation) when it is applied to dissymmetric diesters (or ester–amides). This point, as well the incompatibility of normal experimental conditions with base-labile groups, explains the continuing development of this reaction.
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Meeeee 88 Meeeeeee-Meeee Meeeeeeee Meeeeeeee Meeeeeeeeeee[888]
Mee eeee eeeeee eee eeee ee eeeeeeee. Meee, eeeeee eeeeeeeeeeeeeeeeeeeeee ee eeeeeeeeeeeeeee ee –88°M eeeeee eeeeeeeee eeee eeeeeee ee eee eeeeee eeee ee e eeeeeeeeeeeeeee.[888] Meeeeeeee eeeeeeeeeeeeeeeeeeeeee eeeeee eeeeeee eeeeeeeee eee eee eeeeeeeee ee ee eeeeeeeeeeeeeeee eeeeeeee eeee eeee 888 (Meeeee 88),[888] ee eee eee eeeeeeeeeee ee eeeeeeeee α-eeeee-β-eeeeeeeeeeeeee eeee eee eeeeeeeeeeeee eeeeeeeeeeeeee.[888] M eeeeee eeee eeee ee eeeeeeeeeeeeeeeeee eeeeeeee eeeeeeeeeeee eeeeeeee ee eeeee eeeeeee eeee e eeeeeeeeeeeeeeee ee eeee eeeee.[888] M eeeeeee-eeee eeeeeeee eee eeee ee eeee ee eeeeeee eeeeeee eeeeeee ee eeeeeeee eeee eee eeeeeeeeeeeee 8-(eeeeeeeeeeeeee)eeeeeeeeeeeeeee eee -eeeeeeeee.[888]
Meeeee 88 Meeeeeeee Meeeeeeeeeeeeeeeeeeeee Meeeeee Meeeeeeee Meeeeeeeeeee[888]
Me eeeeeeeeeeeee eeeee, eee eeeeeeeee ee eee eeeeeeeeeee eeeeeee ee eeeee eee e M,M-eeeeeeeeeeeeee, eeeeeee ee e eeeeeeeeeee eeeeeeeeee, eee ee eeeee eeeeeeeeee.[888] Mee eeeeeeeeeeeeeeee eee eeee ee eeeeeeeeee ee eeeee ee eeeeeeeeeee[888] ee e Meeeeee eeeee.[888] Meeeeeeeeeeeee eeeeeeeeeee eee ee eeeeeeee ee eeeeeee eee eeeeeeeee ee eeeeeeeeeee. Meee, e eeeeeeee ee eee “eeeeeee” eeeee ee eeeeeeeeeee ee eee eeeeeeee 888 eeeeeee ee eee eeee-eeeeeeeeeee ee e eeeee eeee-eeeee eeeee ee eee eeeeeeee eeeeeeee eeeee 888 eee eeee eeeeeeee (Meeeee 88).[888]
Meeeee 88 Meeeeeeeeeeeeeee Meeeeee Meeeeeeeeeee ee e Meeeeeeee Meeeeeeeeeee[888]
Mee eeee eeee eeeee e Meeeeeeee eeee eee ee eeeeeeeeeeee ee e eeeeee eeeeeeee ee eeeeeee eeeeee ee eeeeee eeeeeeee ee eeee eeeeeeee. Me eeeeeeeeee eeeeeeeeee–eeeeeeeeeee eeeeeeee eee eeee eeeeeee, eee eeeeeeee, ee eee eeeeeeeee eeeeeeeee ee e eeeeeeeeeeee. Me eee eeeeeeee ee eeeeee eeeeeee; eeee eeeeee eeeeeeeee eeeee ee e 8,8-eeeeeeeeeeeeeeeeeeeeee-8-eee 888 (Meeeee 88), eeeeeeeee eeeeeee e eeeeeee eeeeeeeeee eeeeeeeeeee eeeeeeee ee e Meeeeeeee eeeeeeeeeeee (eeeee ee eeeeee eeee eee eeeeeeeee eeeeee eeeeeeeeee).[888] M [8+8]-eeeeeeeeeeeee–Meeeeeeee eeeeeeee eeeee eeeeeeeee eeeeee ee eeeeeeee β-eeeeeeee (8-eee eeeeeeee).[888,888]
Meeeee 88 Meeeee Meeeeeeeee Meeeeeeeee–Meeeeeeee Meeeeeeeeeee Meeeeeee[888]
Meee eeee eee Meeeeeeee eeeeeeeeeeee eee eeee eeeeeee ee eee(eeeeeeeeee), eeee ee ee-M,M′-eeeee eeeeeeeeeeee ee eeeeeeeeeee, eeeee eeeeeee ee eeee eee eeeeeeeeeeeee eeee- eee eee-eeeeeeee eeee 8-eee eeeeeeeeee eeee eeeee eeeeeee.[888] Meeee eeeeeeeeeeee ee eeeeeee eeeeeeee eeeeeeeee, eee Meeeeeeee eeeeeeeeeeee ee eeee ee eee eeeeeeeee ee eee eeeeeee eeeeeeeee eeeeeeee[888] eee ee e eeeee eeeeeeeee ee eeeeeeeeeeeeee M.[888]
Meeeeeeeeeee Meeeeeeee
Meeeee (8M,8eM)-8-eeee-Meeee-8,8-eeeeeeeeeeee-8M-eeeeeee[8,8-e][8,8]eeeeeee-8e(8M)-eeeeeeeeeee (888, M8 = M):[888]
M eeee ee M-eeeeeeeeeeeeeee 888 (M8 = M; 8.88e, 88.8 eeee) eee e-MeMM (8.88e, 88.8 eeee) ee e-MeMM (88 eM) eee eeeeeeee eee 8 e, eeee eeeeee ee ee eee eeeeeeeeeee eeeeeee Me8M (88 eM) eee M8M (8 × 88 eM). Mee eeeeeee eeeee eee eeeeeeeee eeee 8 M MMe eee eeeeeeeee eeee MeMMe (8 × 88 eM). Mee eeeeeee eeeeeeee eeee eeeeee eeee ee 8 M MeM8MM8 (8 × 88 eM) eee eeeee (88 eM), eeeee (MeMM8), eee eeeeeeee eeeeeee e eeeeee eeee (888 eM) eeee eee eeeeee eeeeeee eeee MeMMe (888 eM). Meeeeee ee eee eeeeeee ee eeeee eeee ee eeeeee eeeeeeeeeee eeeee; eeeee: 8.88 e (88%).
References
[94] | Meeeeeee, M. M.; Meeeeeeeee, M. M., Mee. Meeee. (M. M.), (8888) 88, 8. |
[259] | Meeeee, M. M., Me.; Meee, M., M. Mee. Meee., (8888) 88, 8888. |
[297] | Meeeeee, M.; Meeeeeeee, M.; Meeeeeee, M.; Meeeee, M., Meeeeeeeeee Meee., (8888) 88, 8888. |
[311] | Meee, M. M.; Meeeeeeeeee, M. M.; Mee, M.-M.; Meeee, M.; Meeeeeee, M.; Meee, M., Meeeeeeeeee Meee., (8888) 88, 8888. |
[323] | Meeeeeeee, M. M.; Meeáe, M. M.; Meeeeeee, M., M. Mee. Meee., (8888) 88, 8888. |
[488] | Meeeee, M., Meee. Meee. Mee. Mee., (8888) 88, 8888. |
[489] | Meeeeee, M.; Meeeeee, M.; Meeeeeee, M.; Meeeee, M., Meeeeeeeeee Meee., (8888) 88, 8888. |
[490] | Meeeeeee, M.; Meeeeeeee-Meeeeeeee, M.; Meeeeeeeeee, M., Meeeeeeeeee, (8888) 88, 8888. |
[491] | Meeeee Meee, M. M.; Meeeee, M.; Meeeeeeee, M. M.; Meeeeee, M. M.; Meeee, M.; Meeeeee, M., Meeeeee, (8888), 8888. |
[492] | Meee, M. M.; Meeeeeee, M., M. Mee. Meee., (8888) 88, 888. |
[493] | Meeeee Meee, M. M.; Meeee, M. M.; Meeeee, M. M.; Meeeee, M. M.; Meeee, M. M.; MeMee, M., Meeeeee, (8888), 8888. |
[494] | Meee, M.; Meeeee, M.; Meee, M., M. Meee. Mee., Meeeee Meeee. 8, (8888), 8888. |
[495] | Meeee, M.; Mee, M., Meeeeeeee, (8888), 888. |
[496] | Meeeeee, M. M.; Meeeeeee, M. M.; Meeeeeee, M. M.; Meeeee, M. M.; Meeee, M.; Meeeeee, M. M.; Meeee, M.; Meeeee, M., M. Meee. Mee., Meeeee Meeee. 8, (8888), 888. |
[497] | Meeeeeee, M. MeM.; Meee, M.-M., Meeeeee, (8888), 888. |
[498] | Meeeee, M.; Meee, M.; Meeeeeee, M., M. Me. Meee. Mee., (8888) 888, 8888. |
[499] | Meeeee, M.; Meee, M.; Meeeeeee, M., M. Mee. Meee., (8888) 88, 8888. |
[500] | Meeeee, M.; Meee, M., Meeeeeeeeee, (8888) 88, 8888. |
[501] | Meeeeeee, M. M.; Mee, M.; Meeeeeeeee, M.; Mee, M. M., M. Me. Meee. Mee., (8888) 888, 88888. |
Meeeeee Meeeeeeeeee
- 8.Meeeee-Meee, (8888) 8, 888.
- 8.Meeeee-Meee, (8888) 8/8, 888.
- 8.Meeeee-Meee, (8888) 8/8, 888.
- 8.Meeeee-Meee, (8888) 88/8, 888.
- 8.Meeeee-Meee, (8888) 8/8e, 888.
- 8.Meeeee-Meee, (8888) 8/8e, 8888.
- 8.Meeeee-Meee, (8888) M 88-8, 888.
- 8.Meeeee-Meee, (8888) M 8e8, 8888.
- 8.Meeeee-Meee, (8888) M 8e8, 88.
- 8.Meeeee-Meee, (8888) M 8e, 888.
- 8.Meeeee-Meee, (8888) M 8e, 888.