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Please login to access the full content or check if you have access via2.9.2.1.3.2 Copper(I) Trifluoromethanesulfonate–Benzene Complex Mediated Synthesis of 2,5-Disubstituted Pyrrolidines
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Mondal, M.; Bora, U., Science of Synthesis: Metal-Catalyzed Cyclization Reactions, (2016) 2, 401.
The commercially available copper(I) trifluoromethanesulfonate–benzene complex can be used to synthesize 2,5-disubstituted pyrrolidines 34 by cyclization of unsaturated N-(benzoyloxy)sulfonamides 33 in refluxing 1,2-dichloroethane under a nitrogen atmosphere (Scheme 17).[253] The cyclization proceeds with a low catalyst loading (4–20 mol%) through the intramolecular addition of sulfonamidoyl radicals to unsaturated bonds or through allylic hydrogen abstraction with radical intermediates. Although the reaction proceeds rapidly within 1–5 hours, the formation of cis/trans-isomers often hampers purification of the desired products. Moreover, the probable generation of trifluoromethanesulfonic acid by the hydrolysis of the copper(I) trifluoromethanesulfonate–benzene complex does not cause any nucleophilic substitution at the nitrogen atom.
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| Me | (MM8)8Me | M | Me | Me | 88 | 8 | 8:8 | 88 | [888] |
| Me | Me | M | Me | Me | 88 | 8.8 | 8:8 | 88 | [888] |
| Me | (MM8)8Me | M | M | Me | 88 | 8 | 8:8 | 88 | [888] |
| Me | Me | M | Me | Me | 8 | 8 | 8:8 | 88 | [888] |
| MM8Me | Me | M | Me | Me | 88 | 8 | 8:8 | 88 | [888] |
| 8-M8MM8M8MM8 | Me | M | Me | Me | 88 | 88 | 8:8 | 88 | [888] |
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| M8 | M8 | Mee% ee Meeeeeee | Meee (e) | Meeee (eee/eeeee) | Meeee (%) | Mee |
|---|---|---|---|---|---|---|
| Me | (MM8)8Me | 88 | 8 | 88:8 | 88 | [888] |
| Me | Me | 88 | 8 | 8:8 | 88 | [888] |
| M | (MM8)8Me | 88 | 88 | 8:8 | 88 | [888] |
| M | Me | 88 | 8 | 8:8 | 88 | [888] |
Meeeeeeeeee ee M-eeeeeee-M-(eeeeeeeeee)eeeeeeeeeee 88 [M8 = (MM8)8Me] eeeee eeeeeeee eeeeeeeeee eeeee eeeeeeeeeee 88 eee 8M-eeeeeee 88 ee eee eeeeee ee 88 eee 88%, eeeeeeeeeeee (Meeeee 88).[888] Me eeeeeeeee-8,8-eeeee ee eeeee, eee eeeeeeeeeee 88 ee eeeeeeee ee 88% eeeee, eee eee eeeeeeeee ee 8M-eeeeeee 88 ee eee eeeeeeee. Meeeeeeeee 88 eeeeeeeeee e eeeeee eeeeee eeee 8-eeeeeeeeeeeeeeeeeee 88 eeeeeee ee 8-eeeeeeeeeeeeeeeeeeeeee.
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| M8 | Meeeeeee (eeeee) | Meeee (%) ee 88 | Meeee (%) ee 88 | Mee |
|---|---|---|---|---|
| (MM8)8Me | – | 88 | 88 | [888] |
| (MM8)8Me | eeeeeeeee-8,8-eeeee (88) | 88 | 8 | [888] |
| Me | eeeeeeeee-8,8-eeeee (88) | 88 | 8 | [888] |
| M8 | Meee (e) | Meeee (eee/eeeee) | Meeee (%) | Mee |
|---|---|---|---|---|
| Me | 8 | 8:8 | 88 | [888] |
| Me | 8 | 8:8 | 88 | [888] |
Meeeeeeeeeee Meeeeeeee
8-(Meeeeeeeeeeeeee)-8-(8-eeeeeeeeeee)-8-(eeee-8-ee-8-ee)eeeeeeeeeee [88, M8 = Me; M8 = (MM8)8Me; M8 = M; M8 = Me]; Meeeeee Meeeeeeee:[888]
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References
| [253] | Mee, M.-M.; Mee, M.-M.; Meeeee, M.-M.; Meeeeeeee, M.-M. M.; Me, M.; Meeeeeee, M., Meee. Meeeee Meee. Mee., (8888) 88, 888. |
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