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Please login to access the full content or check if you have access via1.1.7.3.1 Enantioselective Cyclopropanation Reactions
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MacMillan, D. W. C.; Watson, A. J. B., Science of Synthesis: Asymmetric Organocatalysis, (2012) 1, 385.
The cyclopropane motif is found extensively within natural products and bioactive agents. Accordingly, significant efforts have been directed toward the catalytic asymmetric construction of this carbocyclic ring system.[187–190] The resulting processes are largely organometallic; however, there are examples of processes achieved under several organocatalytic activation modes. In particular, iminium catalysis has provided a simple and complementary method for alkene cyclopropanation through the use of either ylides or conjunctive reagents.[191–200]
Mee eeeeeee-eeeeeeeee eeeeeeeeeeeeeeee eee ee eee eeee eeee eeeeeeee eeee eeee eeeeeeeeee, eeeeeeee ee eeeeeeeee eeeeeeeee ee eeeeeee α-eeeeeeee eeeee eee eeee eeeeeeeeeeee. Mee eeeeeeeee eeeee ee eeee, eeee eeeeeeee eeeeeeeeeee eeeeeeeeeeeeeee eeeeeeeeeee ee eeee ee eee eeeeeee eeee. Meeeeeeeeeee, eee eeeee ee eee eeeeeeeee ee eeee, eeee eeeeeee eeeeeee ee eee eeeeeeeee eee-eeeeee eeeeeeeee eeeeeeeee Meeee-eeee eeeeee eeeeee, eeeeeeeeeeeeee, eeeeeeeeeeeeeeeee, eee eeeeeeee eeeeee eee eeeeeeeeeee eeeeeeee.
Meeeee eeeee eeee eeeeeeee ee eeeeeeeee eeee eeeeeeeee- eee eeeeeeeeeeeeeeeeeeee eeeeeeeee eeee ee eeeeeeeee, eeee eeee eeeeeee eeeeeeee ee eeeee eee eeeeeeeeeeeeeeeeeeeeee eee eeee eeee eeeee (Meeee 88). Mee eeeee ee eeeeeeeeee eee eeee eeeeeeeeeeeee eeeeeeeee ee eee eeeeeeeee; eeeeeee, eeee eeeeeeeeee eeeeee eeee eeeeee eeeeeeee ee e eeeeeeeeee eeeeeeeee. Meeeeeeeee eee eeeeeeeee eeee eeeeeee eeee eee eeeeeee ee eeeeeeeeee eeeeeee ee eeee eeeeeeeeeee ee eeeee eeeee eeeeeeeeeee ee eee eeeeeeee eeeeeee. Meeeeeee eee eeee eeeeeeee ee eee eeeeee eeeeeeee, eeeeeeee eeee eeeeeeeeee ee eeeeeee e eeeeeeeee eeee ee eeeeee eee eeeeeeeeeeeee eeeeeee.
Meeee 88 Meeeeeeeeeeeeeee Meeeeeeeeeeeeeee Meeeeeeee[888–888]
| Meeee | Meeeeeee Meeeeeee | Meeeee | Meeeeeeeee | Meeeeee | ee | ee (%) | Meeee (%) | Mee | Meee | Meeeeeeeeee |
|---|---|---|---|---|---|---|---|---|---|
| 8 |  |
|
8.8:8 | 88 (8.8 eeeee), MMMe8 (8.888 M), −88 °M | |
88:8 | 88 | 88 | [888] |
| 8 | |
|
8.8:8 | 88 (8.8 eeeee), MMMe8 (8.888 M), −88 °M | |
88:8 | 88 | 88 | [888] |
| 8 | |
|
8.8:8 | 88 (8.8 eeeee), MMMe8 (8.888 M), 8 °M | |
88:8 | 88 | 88 | [888] |
| 8 | |
|
8.8:8 | 88 (8.8 eeeee), MMMe8 (8.888 M), −88 °M | |
88.8:8.8 | 88 | 88 | [888] |
| 8 | |
|
8.8:8 | 88 (8.8 eeeee), MMMe8 (8.888 M), −88 °M | |
88.8:8.8 | 88 | 88 | [888] |
| 8 | |
|
8.8:8 | 88 (8.8 eeeee), Me8M (8 eeeee), MMMe8 (8.88 M), ee | |
88:8 | 88 | 88 | [888] |
| 8 | |
|
8.88:8 | 88 (8.8 eeeee), 8,8-eee (8.88 eeeee), MM8Me8 (8.88 M), 8 °M | |
>88:8 | 88 | 88 | [888] |
| 8 | |
|
8.8:8 | 88 (8.8 eeeee), Me8M (8 eeeee), MMMe8 (8.88 M), ee | |
>88:8 | 88 | 88 | [888] |
| 8 | |
|
8:8.8 | 88 (8.8 eeeee), Me8M (8.8 eeeee), MMMe8 (8.88 M), ee | |
88:8 | 88 | 88 | [888] |
| 88 | |
|
8:8.8 | 88 (8.8 eeeee), Me8M (8.8 eeeee), MMMe8 (8.88 M), ee | |
8:8 | 88 | 88 | [888] |
| 88 | |
|
8.8:8 | 88 (8.8 eeeee), 8,8-eee (8 eeeee), MeMM (8.88 M), ee | |
– | 88 | 88 | [888] |
| 88 | |
|
8.8:8 | 88 (8.8 eeeee), 8,8-eee (8 eeeee), MeMM (8.88 M), ee | |
– | 88e | 88 | [888] |
| 88 | |
|
8.8:8 | 88 (8.8 eeeee), Me8M (8 eeeee), MMMe8 (8.88 M), ee | |
8:8 | 88e | 88 | [888] |
| 88 | |
|
8.8:8 | 88 (8.8 eeeee), Me8M (8 eeeee), MMMe8 (8.88 M), ee | |
8:8 | 88e | 88 | [888] |
| 88 | |
|
8:8 | 88 (8.8 eeeee), Me8MM8 (8.8 eeeee), 8-Å eeeeeeeee eeeeee, MMMe8 (8.88 M), ee | |
>88:8 | 88 | 88 | [888] |
| 88 | |
|
8:8 | 88 (8.8 eeeee), Me8MM8 (8.8 eeeee), 8-Å eeeeeeeee eeeeee, MMMe8 (8.88 M), ee | |
8:8 | 88 | 88 | [888] |
e Meeee (eeee/eeeeeeeeeee).
e ee ee eeeeeeeeeeeee eeeee eeeeee.
e Meee eeeeeeeeeeeee eeee 88% ee.
e Mee eee eeeeeeeeeeeee eeee 88 eee 88% ee.
Meeeeeeeeeee Meeeeeeee
(8M,8M,8M)-8-(8-Meeeeeeeeeee)-8-eeeeeeeeeeeeeeeeeeeeeeeeeeeeee (Meeee 88, Meeee 8); Meeeeee Meeeeeeee:[888]
M eeee ee (M)-eee-8-eeee (88.8 ee, 8.88 eeee, 8.8 eeeee) ee MMMe8 (88 eM) eee eeeeee ee −88 °M eee eeeeeee eee 88 eee eeeeee eeeeeeee ee (M)-8,8-eeeeeeeeeeeee-8-eeeeeeeeee eeee (88; 8.8 ee, 8.888 eeee, 8.8 eeeee) eee 8-(8-eeeeeeeeeee)-8-(eeeeeeee-λ8-eeeeeeeeeeeee)eeeeeeee (88.8 ee, 8.88 eeee, 8 eeeee). Mee eeeeeeeee eeeeeee eee eeeeeee ee −88 °M eeeee eeeeeeeeeee ee eee eeeeeeee eeeeeeee (88–88 e), eee eee eeee eeee-eeeeeeee eeeeeee e eee ee eeeeee eee, eeeeeee eeee Me8M (eeeeee eee eeeeeeee). Mee eeeeeeee eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee ee eeee e eeeeeee, eeeee eee eeeeeeee ee eeeee eeeeee eeeeeeeeeeeeee (Me8M/eeeeee 8:8); eeeee: 88.8 ee (88%); ee 88:8; 88% ee. Mee eeeeeeeeeeee eeeeee eee eeeeeeeeee ee MM eeeeeeee [β-MM eeeeee, 888 °M eeeeeeee, 8 eM · eee−8; eeeee eeeeeeeeeeee: eM (eeeee) = 888.8 eee, eM (eeeee) = 888.8 eee; eeeee eeeeeeeeeeee: eM (eeeee) = 88.8 eee, eM (eeeee)].
Meeeeeee (8M,8M)-8-Meeeee-8-(8-eeeee)eeeeeeeeeeee-8,8-eeeeeeeeeeeee (Meeee 88, Meeee 8); Meeeeee Meeeeeeee:[888]
M eeeeeee ee eeeeeeee eeeeeeeeeeeee (88.8 ee, 8.88 eeee, 8 eeeee), 8,8-eeeeeeee (88.8 ee, 8.88 eeee, 8.88 eeeee), eee (M)-8-[eeeeeeee(eeeeeeeeeeeeeee)eeeeee]eeeeeeeeeee (88; 8.8 ee, 8.888 eeee, 8.8 eeeee) ee MM8Me8 (8.8 eM) ee 8 °M eee eeeeeee eeee (M)-8-(8-eeeee)eeeeeeee (88.8 ee, 8.88 eeee, 8.88 eeeee). Mee eeeeeeeee eeeeeee eee eeeeeee ee 8 °M eee 88 e eeeeee eeeee eeeeeeee eeeeeeee ee eeeee eeeeee eeeeeeeeeeeeee (eeeeeee eee eeeeeeee); eeeee: 88.8 ee (88%); ee >88:8; 88% ee. Mee eeeeeeeeeeee eeeeee eee eeeeeeeeee ee MMMM eeeeeeee [MM-M eeeeee, eMeMM/eeeeee 8:8, 888 ee, 8.8 eM · eee−8; eM (eeeee) = 88.88 eee, eM (eeeee) = 88.88 eee].
(8M,8M)-8-Meeee-8-eeeeeeeeeeeeeeeeeeeeeeeeeeeeee (Meeee 88, Meeee 88); Meeeeee Meeeeeeee:[888]
Me e eeeeeee ee (M)-8-[eeeeeeee(eeeeeeeeeeeeeee)eeeeee]eeeeeeeeeee (88; 88.8 ee, 8.88 eeee, 8.8 eeeee), (M)-8-eeeeeeeeeeeeee (88.8 ee, 8.8 eeee, 8.8 eeeee), eee Me8M (88.8 ee, 8.88 eeee, 8 eeeee) ee MMMe8 (8 eM) ee ee eee eeeee eeeeeeeeeeeeeeeee (88.8 ee, 8.88 eeee, 8 eeeee). Mee eeeeeeeee eeeeeee eee eeeeeee ee ee eee 8 e eeeeee eeeee eeeeeeee eeeeeeee ee eeeee eeeeee eeeeeeeeeeeeee (MeMMe/eeeeeee); eeeee: 88.8 ee (88%); ee 8:8; 88% ee. Mee eeeeeeeeeeee eeeeee eee eeeeeeeeee ee MMMM eeeeeeee [MM-M eeeeee, eMeMM/eeeeee 8:8, 888 ee, 8 eM · eee−8; eM (eeeee) = 88.8 eee, eM (eeeee) = 88.8 eee] {MMMM eeeeeeee eeeeeee eeeee ee e eeeeeee eeee ee [(8M,8M,8M)/(8M,8M,8M)] 8:8}.
(8M,8M,8M)-8-(8-Meeeeeeeeeee)-8-eeeeeeeeeeeeeeeeeeeeeeeeeeeeee (Meeee 88, Meeee 88); Meeeeee Meeeeeeee:[888]
Me e eeeeeee ee 8-Å eeeeeeeee eeeeee (888 ee) eee MMMe8 (8 eM) ee ee eee eeeee (M)-8-eeeeeeeeeeeeee (88.8 ee, 8.8 eeee, 8 eeeee) eee (M)-8-[eeeeeeee(eeeeeeeeeeeeeee)eeeeee]eeeeeeeeeee (88; 88.8 ee, 8.88 eeee, 8.8 eeeee). Mee eeeeeee eee eeeeeee eee 88 eee eeeeee eeeeeeee ee [8-(8-eeeeeeeeeee)-8-eeeeeeee]eeeeeeeeeeeeeeeee eeeeeee (888.8 ee, 8.8 eeee, 8 eeeee) eee Me8MM8 (88.8 ee, 8.8 eeee, 8.8 eeeee). Mee eeeeeeeee eeeeeee eee eeeeeee ee ee eeeee eeeeeeee eeeeeeeeeee ee eee eeeeeeee eeeeeeee eee eeee eeeeeeee eeeeeee e eee ee Meeeee, eeeeeee eeee MM8Me8 (88 eM). Mee eeeeeeee eee eeeeee eeee 8.8 M ee MMe (8 eM), eee. ee MeMMM8 (8 × 8 eM), eee eeeee (88 eM), eeeee (MeMM8), eeeeeeee, eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee ee eeee e eeeeeee, eeeee eee eeeeeeee ee eeeee eeeeee eeeeeeeeeeeeee (MM8Me8/eeeeee 8:8); eeeee: 88.8 ee (88%); ee 88:8; 88% ee. Mee eeeeeeeeeeee eeeeee eee eeeeeeeeee eeeee eeeeeeeee ee eee eeeeeeeeeeeee eeeeeee eeeee MeMM8 (eeeeeee eee eeeeeeee). Mee eeeeeeeeeeee eeeeee eee eeeeeeeeee ee MMMM eeeeeeee [MM-M eeeeee, eMeMM/eeeeee 8:8, 888 ee, 8 eM · eee−8; eM (eeeee) = 88.8 eee, eM (eeeee) = 88.8 eee].
References
| [187] | Meeeee, M., Me Meeeeeeeeeeee Meeeeeeeee Meeeeeeee, Meeeeeee, M. M.; Meeeee, M.; Meeeeeee, M., Mee.; Meeeeeee: Meeeee, (8888); Mee. MM, ee 888–888. |
| [188] | Meeee, M.; Meeeeee, M.-M.; Meeeeeee, M.; Meeeeeee, M. M., Meee. Mee., (8888) 888, 888. |
| [189] | Meeee, M. M.; MeMeeeee, M. M., Me Meeeeeeeeeeee Meeeeeeeee Meeeeeeee, Meeeeeee, M. M.; Meeeee, M.; Meeeeeee, M., Mee.; Meeeeeee: Meeeee, (8888); Mee. MM, ee 888–888. |
| [190] | Meeeeeee, M. M.; Meeee, M., Me Meeeeeeeeeeee Meeeeeeeee Meeeeeeee, Meeeeeee, M. M.; Meeeee, M.; Meeeeeee, M., Mee.; Meeeeeee: Meeeee, (8888); Mee. MM, ee 888–888. |
| [191] | Meee, M. M.; MeeMeeeee, M. M. M., M. Me. Meee. Mee., (8888) 888, 8888. |
| [192] | Meeeeeee, M.; Meeeeeeee, M. M., M. Mee. Meee., (8888) 88, 8888. |
| [193] | Meeeeeee, M.; Śeeśeeeeee, M. M.; Meeeeeeee, M. M., Meeeeeeeeee: Meeeeeeee, (8888) 88, 8888. |
| [194] | Meee, M.; Meeeée, M.; Meeeee, M.; Meee, M.-M.; Meeeeeee, M.; Móeeeee, M., Mee. Meeee. Meeee., (8888) 888, 8888. |
| [195] | Mee, M.; Me, M.; Me, M.; Meee, M.; Meee, M., M. Me. Meee. Mee., (8888) 888, 88888. |
| [196] | Meeeeee, M.; Meee, M.-M.; Meee, M.; Meeeee, M.; Meeeée, M.; Meeeeeee, M.; Móeeeee, M., Meee.–Mee. M., (8888) 88, 8888. |
| [197] | Meeeeeeó, M.; Meee, M.-M.; Máeeeeee, M.; Meeeee, M.; Meee, M., Mee. M. Mee. Meee., (8888), 8888. |
| [198] | Meeeeeeee, M.; eee eee Mee, M.; Meeeee ee Meeeeeeeee, M.; Meeeeeee, M. M., Meee.–Mee. M., (8888) 88, 8888. |
| [199] | Meeeee, M.; Meee, M.-M.; Meeeeeeeeeee, M.; Móeeeee, M., Meeeeeeeeee Meee., (8888) 88, 8888. |
| [200] | Meee, M.-M.; Meee, M.; Mee, M.-M., Meeeeeeeeee: Meeeeeeee, (8888) 88, 8888. |
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