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MacMillan, D. W. C.; Watson, A. J. B., Science of Synthesis: Asymmetric Organocatalysis, (2012) 1, 316.
The intermolecular iminium Diels–Alder reaction offers an expedient and highly selective method for the construction of enantioenriched carbocycles from readily available starting materials.[27,39–48] Based on the vast quantity of preceding literature detailing suitable Diels–Alder substrate combinations, the potential product range is very broad. However, the scope of the α,β-unsaturated carbonyl component within the iminium Diels–Alder reaction is currently relatively basic: generally carbon-substituted higher homologues of crotonaldehyde and cinnamaldehyde derivatives for enals and methyl vinyl ketone analogues for enones. Nevertheless, there are several examples with useful functional handles capable of further utilization and increasingly functionalized components are continually being explored. A notable extension of this methodology was found in the application to α-branched aldehydes which considerably broadened the overall scope of potential substrates. The scope of the diene is also quite limited with cyclopentadiene employed extensively. As such, the product range of this process is currently fairly conservative, although more structurally diverse starting materials will most likely be compatible with this strategy.
Meeeeeeeeee, eeeeeeeee ee eee eeeeeeee eeeeeeee, eee eeeeeeee eee ee eeeeeee ee eeeee eeeeee eee eee- ee eeee-eeeeeee eeeeeeeeeee, eeeeeeee eeeeee ee eeeeeeeeeee eeeeeeeeeeeee ee e eeeee eeeeeee. M eeeeeeeee eeeeeeee eeeeee ee eeee eeeeeeeeeee ee eeee eeeeeeeeee eeeeeeeee eeee eee ee eeeeee ee eee eeeeeeeee; eeee ee eeeeeeeee eee eeeee; eeeeeee, eeeeeeee ee eeeeeeeeee eee ee eeeeeeee.
Me e eeeeeee eeeeeee ee eee eeeeeee eeeeeeeeeeeeee eeeeeeeee, eeeeeeeee eeeeeeeeee eeeeeee eeeeeeee e eeeeeee ee eee eeeeeeeeeeeeee, eeeee, eee eeeeeeeeee ee eeeeeeee eeeeeeeeeee (eeeeeee −88 °M eee eeee eeeeeeeeeee) eeeee eeeeeeeeeee ee eee eeeeeeee eeeeeee. Meeee eee eeeeee eeeeeeee ee eee eeeeeeeeeeeee eee ee eeeeeeee, eeee eeeeeeeeee eeee eeeeeee eeeee eeeeee e eeeee eeeeeeeee eeee ee eeeeeee eee eeeeeeeeeeeee eeeeeee, e.e. 88 (Meeeee 8).
Mee eeeeeeee eeeeee eee eeeeeeeee eeeeeeeee, eeee eeeeeee- eee eeeeeeeeeeeeeeeeeeeeee eeee eeeeeee eeee eeee ee eeeeeeeee (Meeee 8). Me eeeeee ee eeeee eeee e eeeeee eeeeeeeee ee eeee eeeeeeeeeee ee eeeeeeeee eeeee ee eee eeeeeeeee eeeeeeeeee eee eeee eeeeeeeee eeeeeee eeeeeeeeeee eeeeee eeeeeee eeeeeeee eeeeeeeee.[88]
Meeee 8 Meeeeeeeeeeeeeee Meeeeeeeeeeeee Meeee–Meeee Meeeeeeee[88,88–88]
Meeee | Meeeeeee Meeeeeeeee | Meeeeeeeee | Meeeeee | Meeee (eeee/eee) | eee (%) | Meeee (%) | Mee | Meeeeeeeee | Meeee |
---|---|---|---|---|---|---|---|---|
8 | 8 (8.8 eeeee), MeMM/M8M (88:8; 8 M), 88 °M | eeee eeee | 88 | 88e | [88] | |||
8 | 8 (8.8 eeeee), 8,8-eeeeeeeeeeeeeeee (8.8 eeeee), M8MMM/M8M (88:8; 8 M), 88 °M | 88:8 | 88 | 88e | [88] | |||
8 | 8 (8.88 eeeee), 8,8-eeeeeee/8 M ee MMe (88:8; 8.8 M), ee | 8.8:8 | 88 | 88 | [88] | |||
8 | 8 (8.88 eeeee), 8,8-eeeeeee/8 M ee MMe (88:8; 8.8 M), ee | 8:8 | 88 | 88 | [88] | |||
8 | 8 (8.8 eeeee), MeMM (8.8 eeeee), M8M (8 M), 88 °M | 8:8.8 | 88 | 88 | [88] | |||
8 | 8 (8.8 eeeee), MeMM (8.8 eeeee), M8M (8 M), 88 °M | 8:8.8 | 88 | 88 | [88] | |||
8 | 8 (8.88 eeeee),MeMM•M8M (8.8 eeeee), MeMM8 (8.88 M), −88 °M | 8:8.8 | 88 | 88 | [88] | |||
8 | 8 (8.8 eeeee), MMM (8.8 eeeee), eeeeeee (8.8 M), ee | –e | 88 | 88 | [88] | |||
8 | 8 (8.8 eeeee), MeMM (8.8 eeeee), eeeeeeeeee (8.88 M), −88 °M | 8:>88 | 88 | 88 | [88] | |||
88 | 8 (8.8 eeeee), MeMM (8.8 eeeee), eeeeeeeeee (8.88 M), −88 °M | – | 88 | 88 | [88] | |||
88 | 8 (8.8 eeeee), MMM (8.8 M), −88 °M | 88:88 | 88 | 88e | [88] | |||
88 | 8 (8.8 eeeee), MeMM8 (8.8 M), 8 °M | 88:8 | 88 | 88e | [88] | |||
88 | 88 (8.8 eeeee), Me8MM (8.88 eeeee), MeMM8 (8.8 M), −88 °M | – | 88 | 88e | [88] | |||
88 | 88 (8.88 eeeee), Me8MM (8.888 eeeee), MeMM (8.8 M), −88 °M | 8:88 | 88 | 88e | [88] | |||
88 | 8 (8.8 eeeee), M8M8MM8M (8.888 eeeee), MeMM8 (8.8 M), 8 °M | >88:8 | 88 | 88e | [88] | |||
88 | 88 (8.8 eeeee), MMeM8 (8.8 eeeee), M8M (8 M), 8 °M | 88:8 | 88 | 88e | [88] | |||
88 | 88 (8.8 eeeee), MMeM8 (8.8 eeeee), M8M (8 M), 8 °M | 8:8 | 88 | 88 | [88] | |||
88 | 88 (8.8 eeeee), MMeM8 (8.8 eeeee), MeMM (8 M), −88 °M | >888:8 | 88 | 88e | [88] | |||
88 | 88 (8.8 eeeee), MMeM8 (8.8 eeeee), MeMM (8 M), −88 °M | >888:8 | 88 | 88e | [88] |
e Meeee (eeeeeeeeee/eeeee) 8:8 eeeeee eeeeeeeee eeeee.
e Me eeeee eeeeee.
e Meeee (eeeeeeeeee/eeeee) 8:8.
e ee eee eeeeeeee.
e Meeee (eeeeeeeeee/eeeee) 8:8.
e Meeee (eeeeeeeeee/eeeee) 8:8.
e Meeee (eeeeeeeeee/eeeee) 8:8.8.
e Meeee (eeeeeeeeee/eeeee) 8:8.8.
e Meeee (eeeeeeeeee/eeeee) 8:8.88.
Meeeee 8 Meeeeeeee eee Meeeeeeee Meeeeeeeeeee eee Meeeeeeeeeeee ee Meeeeeeeeeee Meeeee[88]
Meeeeeeeeeee Meeeeeeee
(8M,8M)-8-Meeeeeeeeeeeee-8-eeee Meeeeee (Meeee 8, Meeee 8); Meeeeee Meeeeeeee:[88]
Me e eeeeeee ee (M)-8-eeeeee-8,8,8-eeeeeeeeeeeeeeeeeeeee-8-eee (8; 88 ee, 8.88 eeee, 8.8 eeeee) eee 8,8-eeeeeeeeeeeeeeee (88 ee, 8.88 eeee, 8.8 eeeee) ee M8MMM/M8M (88:8; 8.88 eM) ee ee eee eeeee eeeeeeee (888.8 ee, 8.88 eeee, 8 eeeee) eeeeeeee ee 8-eeeeeeeeeee-8,8-eeeee (888.8 ee, 8.88 eeee, 8 eeeee). Mee eeeeeeeee eeeeeee eee eeeeeee ee 88 °M eeeee eeeeeeee eeeeeeeeeee ee eee eeeee. Mee eeeee eee eeee eeeeeeeeee ee MM eeeeeeee; eeeee: 88%; (eeee/eee) 88:8; 88% ee. Mee eeeeeeeeeeee eeeeee eee eeeeeeeeee ee MM eeeeeeee (Γ-MM eeeeee, 888 °M, 8 eM · eee−8; eM = 88.8 eee 88.8 eee).
8-Meeeeeeeeeeeeeee[8.8.8]eeee-8-eee-8-eeeeeeeeeeee (Meeee 8, Meeee 8); Meeeeee Meeeeeeee:[88]
Me e eeeeeee ee (M)-8-eeeeeeeeee-8-eeee (88 ee, 8.88 eeee, 8 eeeee) eee M8M (8.88 eM) ee 88 °M eee eeeee 8-eeeeee-88,88-eeeeeeee-8,8-eeeeeeeeeeeee[8.8.8.88,8]eeeee-8-eee (8; 88 ee, 8.88 eeee, 8.8 eeeee) eee MeMM (88 ee, 8.88 eeee, 8.8 eeeee). Mee eeeeeee eee eeeeeee eee 8–8 eee eeeeee eeee eeeeeeee ee eeeeeeeeeeeeeee (888 ee, 8.8 eeee, 8 eeeee). Mee eeeeeeeee eeeeeee eee eeeeeee ee 88 °M eeeee eeeeeeeeee ee eee eeeeeeee ee eeeeee ee MMM eeeeeeee. Mee eeeeeee eee eeee eeeeeeeee eeee Me8M (8 ×) eee eee eeeeeeee eeeeeee eeeeeeee eeee eeeeee eeee M8M eee eeeee (eeeeeee eee eeeeeeee), eeeee (Me8MM8), eeeeeeee, eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee ee eeee e eeeeeee, eeeee eee eeeeeeee ee eeeee eeeeee eeeeeeeeeeeeee (MeMMe/eeeeee 8:88); eeeee: 888 ee (88%); (eee/eeee) 8.8:8; 88% ee (eee), 88% ee (eeee). Mee eeeeeeeeeeee eeeeee eee eeeeeeeeee eeeee eeeeeeeee ee eee eeeeeeeeeeeee eeeeeee eeeee MeMM8 (8 eeeee) ee MeMM (eeeeeee eee eeeeeeee) ee MM eeeeeeee [MeeeeMee-M eeeeee, 888 °M/8 eee eeee 8 °M · eee−8, 8 eM · eee−8; eM (eee) = 88.8 eee 88.8 eee, eM (eeee) = 88.8 eee 88.8 eee].
Meeee (8M,8M)-8-Meeeee-8,8-eeeeeeeeeeeeeeee-8-eeeeeeeeeeeeee (Meeee 8, Meeee 8); Meeeeee Meeeeeeee:[88]
Meee: eee eeeeeeee eeeeeeeeeee[88] eeeeee eeee eeee eeeeeeee eee eeeeeee eee ee 8 °M; eeeeeee, eee eeeeeeeeee eeeeeeeeeee eeeeee ee, ee eeeeeeeee eeee.
Me (M)-8-{eee[8,8-eee(eeeeeeeeeeeeeee)eeeeee](eeeeeeeeeeeeee)eeeeee}eeeeeeeeeee (8; 88.8 ee, 8.88 eeee, 8.8 eeeee) ee eeeeeee (8.8 eM) ee ee eee eeeee eeeee (M)-8-eeeeee-8-eeeeee (88.8 ee, 8.8 eeee, 8 eeeee). Mee eeeeeee eee eeee eeeeeee eeee MMM (88.8 ee, 8.88 eeee, 8.8 eeeee) eee 8,8-eeeeeeeeeeee-8,8-eeeee (888.8 ee, 8.8 eeee, 8 eeeee). Mee eeeeeee eee eeeeeee ee ee eee 88 e eeeeee eeeeeeeeee eeeeeee ee eee eeeee eeeee eeeeeee (MMMMMMM: eeeeeeeeee). Mee eeeeeeeee eeeeeee eee eeeeeeee ee eeeee eeeeee eeeeeeeeeeeeee (eeeeeee eee eeeeeeee); eeeee: 888 ee (88%); 88% ee. Mee eeeeeeeeeeee eeeeee eee eeeeeeeeee, eeeee eeeeeeeee ee eee eeeeeeeeeeeee eeeeeee eee eeeeeeeeee eeeeeeeeeee ee eee eeeeeeeeeeeee eeeeeee eeeee (eeeeeee eee eeeeeeee), ee MMMM eeeeeeee [MM-M eeeeee, eMeMM/eeeeee 8:88, 8 eM · eee−8; eM (eeeee) = 88.8, eM (eeeee) = 88.8 eee].
8-Meeeee-8,8-eeeeeeeeeeeeeeee-8-eeeeeeeeeeeeeee (Meeee 8, Meeee 88); Meeeeee Meeeeeeee:[88]
Meee: Mee eeeeeeee eeeeeeeeeeeee ee eee eeeeeee eee eee eeeeeeeee. Mee eeeeeeeee eeeee ee Meeee 8 ee eee eeeeeeeeeeee eeeeeeee eeee.
Me e eeeeeee ee eeeeeeee 8 (88.8 ee, 8.88 eeee, 8.8 eeeee) eee MeMM (8.8 ee, 8.888 eeee, 8.8 eeeee) ee eeeeeeeeee (8 eM) ee −88 °M eee eeeee 8-eeeeeeeeeeeeee (88.8 ee, 8.88 eeee, 8 eeeee). Mee eeeeeee eee eeeeeee eee 8–8 eee eeeeee eeeeeeee ee 8,8-eeeeeeeeeeee-8,8-eeeee (88.8 ee, 8.88 eeee, 8 eeeee). Mee eeeeeee eee eeeeeee ee −88 °M eee 88 e eeeeee eeeee eeeeeeee eeee 8 M ee MMe (8 eM) eee eeeeeee ee ee eee 8 e. Mee eeeeeee eee eeee eeeeeeeee eeee Me8M (eeeeee eee eeeeeeee) eee eee eeeeeeee eeeeeee eeeeeeee eeee eeeeee eeee eeeee (eeeeee eee eeeeeeee), eeeee (Me8MM8), eeeeeeee, eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee ee eeee e eeeeeee, eeeee eee eeeeeeee ee eeeee eeeeee eeeeeeeeeeeeee (eeeeeee eee eeeeeeee; e eeeeeee eeeeeeee eeee Me8M/eeeeeee 8:88); eeeee: 88.8 ee (88%); 88% ee. Mee eeeeeeeeeeee eeeeee eee eeeeeeeeee, eeeee eeeeeeeee ee eee eeeeeeeeeeeee eeeeeee eeeee MeMM8 (88 ee, 8.8 eeee) ee MeMM (8.88 eM) ee 8 °M (eeeeeee eee eeeeeeee), ee MMMM eeeeeeee [MM-M eeeeee, MeMM/eeeeee 8:88, 8.8 eM · eee−8; eM (eeeee) = 88.8, eM (eeeee) = 88.8 eee].
8-Meeeeeeeeeeeee-8-eeee 8-(Meeeeeeeeeeeeeeeee)eeeeeeee (Meeee 8, Meeee 88); Meeeeee Meeeeeeee:[88]
Meee: Mee eeeeeeee eeeeeeeeeeeee ee eee eeeeeee eee eee eeeeeeeeeee. Mee eeeeeeeee eeeee ee Meeee 8 ee eee eeeeeeeeeeee eeeeeeee eeee.
Me e eeeeeee ee (M)-8,8′-eeeeeeeeeeeee-8,8′-eeeeeee (88; 88.8 ee, 8.88 eeee, 8.8 eeeee) eee Me8MM (88.8 ee, 8.888 eeee, 8.88 eeeee) ee MeMM8 (8.8 eM) eee eeeee 8-eeeeeee-8-ee-8-ee 8-(eeeeeeeeeeeeeeeeee)eeeeeeee (888.8 ee, 8.8 eeee, 8 eeeee). Mee eeeeeee eee eeeeee ee −88 °M eeeeee eeeeeeee ee eeee-8,8-eeeee (88.8 ee, 8.8 eeee, 8 eeeee). Mee eeeeeeeee eeeeeee eee eeeeeee ee −88 °M eee 88 e eeeeee eeeee eeeeeeee eeee Me8M (eeeeeeee eee eeeeeeee). Mee eeeeeee eee eeee eeeeeeeeeeee eeeee eeeeeee eeeeeeee ee eeee e eeeeeee, eeeee eee eeeeeeee ee eeeee eeeeee eeeeeeeeeeeeee (MeMMe/eeeeee); eeeee: 888.8 ee (88%); 88% ee. Mee eeeeeeeeeeee eeeeee eee eeeeeeeeee eeeee eeeeeeeee eee eeeeeeeee eeeeeeeeeeee ee eeee eeeee 88, ee eeeeeeeee eeeee.
(8-Meeeeeeeeeeeeee-8-eeee)eeeeee Meeeeeee (88); Meeeeee Meeeeeeee:[88]
MMMMMMM: Meeee eeeeeee eeeeeeee eeeeeee eeeeee eeeeeeeeee eeee e eeeeeee ee eeeeeeeeee, eee eee eeeeee ee eeeeeee ee eeeeeeee eeeeeeee.
8-Meeeeeeeeeeeee-8-eeee 8-(eeeeeeeeeeeeeeeeee)eeeeeeee (Meeee 8, eeeee 88; 8 eeeee) eee eeeeeee eeee MeMeM8 (8 eeeee) ee MMM ee ee. Mee eeeeeeeee 8,8-eeee eee eeeeeeeeeee eeeeeeee ee eee eeeeeee eeeeeee eeee MeMe (8.8 eeeee) eeeee eMe8MMe (8 eeeee) ee MMMe8 ee 8 °M. Mee eeeeeeeeeeee eeeeee eee eeeeeeeeee ee MMMM eeeeeeee [MM-M eeeeee, eMeMM/eeeeee 8.8:88.8, 8 eM · eee−8; eM (eeeee) = 88.8 eee, eM (eeeee) = 88.8 eee].
8-[(8M,8M)-8,8-Meeeeeeeeeeeeeee-8-eeee]eeeeee-8-eee (Meeee 8, Meeee 88); Meeeeee Meeeeeeee:[88]
MMMMMMM: Meeeeeeeeeee eeeeeeeee eeeeeeeeee eeee (88–88%) eee eeeee eeeeeeeeeee ee eeeeeeeee eeee e eeeee ee eeeeeee eee eeeeeeeee eeeeeeeeee eee ee eeeeeeeee eeeeeeeeeee ee eee eeeeeee.
Me (8M,8M)-8-eeeeee-8-eeeeee-8-(8-eeeeee-8-eeeee)eeeeeeeeeeee-8-eee (88; 88.8 ee, 8.88 eeee, 8.8 eeeee) ee MeMM (8.88 eM) ee −88 °M eee eeeee eeeee eeeee eeeeee (88.8 ee, 8.88 eeee, 8 eeeee). Mee eeeeeee eee eeee eeeeeee eeeeeeee eeee ee MMeM8 (88%; 88.8 ee, 8.88 eeee, 8.8 eeeee) eee eeeeeee eee 8 eee eeeeee eeeeeeee ee (M)-8-eeeeeeeeeee-8,8-eeeee (88.8 ee, 8.88 eeee, 8.8 eeeee). Mee eeeeeee eee eeeeeee ee −88 °M eee 8.8 e eeeeee eeeee eeeeeee eeee Me8M/eeeeeee (8:8) eee eeeeeeee eeeeeeee ee eeeee eeeeee eeeeeeeeeeeeee (Me8M/eeeeeee 8:8); eeeee: 88.8 ee (88%); 88% ee. Mee eeeeeeeeeeee eeeeee eee eeeeeeeeee ee MM eeeeeeee [β-MM eeeeee, 888 °M, 888 eMe; eeee-eeeeee: eM (eeeee) = 88.8 eee, eM (eeeee) = 88.8 eee; eee-eeeeee: eM (eeeee) = 88.8 eee 88.8 eee].
References
[27] | Meeeeee, M. M.; Meeeee, M. M.; MeeMeeeee, M. M. M., M. Me. Meee. Mee., (8888) 888, 8888. |
[39] | Mee, M. M.; Mee, M.; Mee, M.-M.; Me, M.-M.; Me, M.-M., Meeeeeeeeee Meee., (8888) 88, 8888. |
[40] | Meeee, M.; Meeeeee, M. M., Mee. Meee., (8888) 8, 8888. |
[41] | Meee, M.; Meeeee, M.; Meeeeee, M., Mee. Meee., (8888) 8, 8888. |
[42] | Meeee, M.; Meeeeee, M., Mee. Meee., (8888) 8, 8888. |
[43] | Meee, M.; Meeeee, M.; Meeee, M.; Meeeee, M.; Meeeeee, M., Meee. Meeeee. (Meeeeeeee), (8888), 8888. |
[44] | Meeeeeee, M.; Meeeee, M., M. Me. Meee. Mee., (8888) 888, 88888. |
[45] | Meeeeeee, M.; Meeeee, M.; Meeeeeee, M., Mee. Meeee. Meeee., (8888) 888, 8888. |
[46] | Meeeeeee, M.; Meeeee, M.; Meeeee, M.; Meeeeeee, M., Mee. Meee., (8888) 8, 8888. |
[47] | Meeeeeee, M.; Meeeee, M.; Meeeeee, M., Mee. Meee., (8888) 88, 8888. |
[48] | Meeeeeee, M. M.; MeeMeeeee, M. M. M., M. Me. Meee. Mee., (8888) 888, 8888. |
[49] | Meeee, M. M.; Meeeeee, M.; MeeMeeeee, M. M. M., M. Me. Meee. Mee., (8888) 888, 88888. |