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Wirth, T.; Singh, F. V., Science of Synthesis Knowledge Updates, (2017) 1, 419.
In 2011, Feng and co-workers reported an asymmetric catalytic aminochlorination of α,β-unsaturated γ-oxo esters 40 using N,N-dichloro-4-toluenesulfonamide/4-toluenesulfonamide (1:1) as reagent and the complex (1:1) of ligand 39 and scandium(III) trifluoromethanesulfonate as catalytic system in dichloromethane (Scheme 21). The reaction products 41 are isolated in excellent yields with up to 99% ee and dr >99:1.[46] It was demonstrated from mechanistic studies that N-chloro-4-toluenesulfonamide, formed in situ from N,N-dichloro-4-toluenesulfonamide and 4-toluenesulfonamide, is the key reactive species in this catalytic approach.[46]
Meeeee 88 Meeeeeeeee Meeeeeeee Meeeeeeeeeeeeeeee ee Meeeeee Meeee M-Meeeee-8-eeeeeeeeeeeeeeeeee[88]
M8 | M8 | ee (%) | ee (%) | Meeee (%) | Mee |
---|---|---|---|---|---|
Me | Me | 88:8 | 88 | 88 | [88] |
Me | Me | 88:8 | 88 | 88 | [88] |
8-MeMM8M8 | Me | 88:8 | 88 | 88 | [88] |
8-Mee | Me | 88:8 | 88 | 88 | [88] |
8-MM8M8 | Me | 88:8 | 88 | 88 | [88] |
8-MeM8M8 | Me | 88:8 | 88 | 88 | [88] |
8-MeM8M8 | Me | 88:88 | 88 | 88 | [88] |
8-M8MM8M8 | Me | 88:8 | 88 | 88 | [88] |
8,8-Me8M8M8 | Me | 88:88 | 88 | 88 | [88] |
8-eeeeeeee | Me | >88:8 | 88 | 88 | [88] |
8-eeeee | Me | >88:8 | 88 | 88 | [88] |
M eeeeeeeee eeeeeeeeeeeeeeeee ee eeeeeeeee 88 eee eeee eeeeeeee eeeee eeeeeee eeeeeeee eeeeeeeeee eee eeeeeeeeeeeeeeee eeeeeeee 88 eee eeeeeeee ee eeeeeeeee eeeee eeee ee ee 88% ee eee ee >88:8 (Meeeee 88).[88] Mee eeeeeeee eeeee ee eeeeeeeeee ee eeee eee eeee eeeeeeee eeeeeee (MeMMMe) ee eee eeeeee ee eeeeeeee eee eeeeeeee ee eee eeeeeeee eeeee.[88]
Meeeee 88 Meeeeeeeee Meeeeeeee Meeeeeeeeeeeeeeee ee Meeeeeeee Meeee M-Meeeee-8-eeeeeeeeeeeeeeeeee[88]
Me8 | Me8 | ee (%) | ee (%) | Meeee (%) | Mee |
---|---|---|---|---|---|
Me | Me | >88:8 | 88 | 88 | [88] |
Me | 8-Mee | >88:8 | 88 | 88 | [88] |
Me | 8-Mee | >88:8 | 88 | 88 | [88] |
Me | 8-MM8M8 | >88:8 | 88 | 88 | [88] |
Me | 8-MeM8M8 | >88:8 | 88 | 88 | [88] |
Me | 8-MeM8M8 | >88:8 | 88 | 88 | [88] |
Me | 8-MeMM8M8 | >88:8 | 88 | 88 | [88] |
Me | 8-M8MM8M8 | 88:8 | 88 | 88 | [88] |
Me | 8-M8MM8M8 | >88:8 | 88 | 88 | [88] |
Me | 8-eeeeeeee | >88:8 | 88 | 88 | [88] |
Me | 8,8-Me8M8M8 | >88:8 | 88 | 88 | [88] |
8-Mee | Me | 88:8 | 88 | 88 | [88] |
8-Mee | Me | 88:8 | 88 | 88 | [88] |
8-Mee | Me | 88:8 | 88 | 88 | [88] |
8-MM8M8 | Me | >88:8 | 88 | 88 | [88] |
8-MeM8M8 | Me | >88:8 | 88 | 88 | [88] |
8-MeM8M8 | Me | >88:8 | 88 | 88 | [88] |
8-MeMM8M8 | Me | >88:8 | 88 | 88 | [88] |
8-MeM8M8 | Me | >88:8 | 88 | 88 | [88] |
8-M8MM8M8 | Me | >88:8 | 88 | 88 | [88] |
8,8-Me8M8M8 | Me | >88:8 | 88 | 88 | [88] |
8-eeeeeeee | Me | >88:8 | 88 | 88 | [88] |
MM=MMMe | Me | 88:8 | 88 | 88 | [88] |
8-MeMM8M8 | Me | >88:8 | 88 | 88 | [88] |
e | ee (%) | Meeee (%) | Mee |
---|---|---|---|
8 | 88 | 88 | [88] |
8 | 88 | 88 | [88] |
Meeeeeeeeeee Meeeeeeee
α-Meeeee-β-(eeeeeeeeee) Meeeeee 88 eee 88; Meeeeee Meeeeeeee:[88]
M eeeeeee ee eeeee 88 ee 88 (8.8 eeee, 8.8 eeeee), 8.888 M 88/Me(MMe)8 ee MMM (8 μM, 8.88 eee%), 8-Å eeeeeeeee eeeeee (88 ee), MeMMe8 (8.88 eeee, 8.8 eeeee), eee MeMM8 (8.88 eeee, 8.8 eeeee) eee eeeeeeee ee MM8Me8 (8.8 eM) eee eeeeeee ee 88 °M eeeee M8. Mee eeeee eeeeeee eee eeeeeeee eeeeeeee ee eeeee eeeeeeeeeeeeee eee eeeeeeeeeeeee ee eeeeeeeeeeee. Mee eeeeeeeeeeee eeeeee eee eeeeeeeeee ee MMMM (Meeeeeeee MM-M, Meeeeeeee MM, Meeeeeeee MM-M, ee Meeeeeeee MM). Mee eeeeeeeeeeeeee eeeee eee eeeeeeeeee ee 8M MMM eeeeeeeeeeee eee MMMM eeeeeeee.
References
[46] | Mee, M.; Mee, M.; Meeee, M.; Meee, M.; Mee, M.; Meee, M., M. Me. Meee. Mee., (8888) 888, 8888. |