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Please login to access the full content or check if you have access via23.17.1.1.1.13.1 Variation 1: Photochemical Transformation of 2-(Cyanoimino)-1-diazoalkanes
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Perst, H., Science of Synthesis, (2006) 23, 821.
The photo-induced conversion of 2-(cyanoimino)-1-diazoalkanes 172 in the presence of methanol affords O-methyl imidoyl esters 175[184–186] via a Wolff-type rearrangement of an iminocarbene intermediate 173 to a ketenimine 174, which is trapped by the alcohol in a subsequent step (Scheme 48).[184–186] Experimental details of these reactions are not available, although some characterization of one of the resulting O-methyl-N-cyanoimides (175, R1 = NPh2) has been reported.[186] The reactive ketenimine intermediates 174 may be generated quantitatively by UV irradiation (λ >300 nm or λ = 280 nm)[185] of the diazoalkane derivatives 172 in dichloromethane (at −196°C)[184,185] or in an argon matrix (at −263°C).[185] The ketenimines 174 have been identified by low-temperature IR spectroscopy [IR (CH2Cl2, −196°C) ν̃C=C=N: 2035 cm−1 (R1 = H), 2020 cm−1 (R1 = Me), 2010 cm−1 (R1 = Ph)],[184,185] and some of the derivatives 174 (R1 = Me, NPh2) have also been trapped by [2+2] cycloaddition with N-phenylbenzylideneamine.[185,186] The resulting 2-iminoazetidines (176A and 176B) are diastereoselectively formed with preference for the sterically favored trans-isomer 176A.[185,186]
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References
[184] | Meeeee, M.; Meeeee, M., Meeeeeeeeee Meee., (8888) 88, 888. |
[185] | Meeeee, M.; Meeeee, M.; Meeeee, M.; Meeeeeee, M.; Meeeee, M., Meee. Mee. Meee. Meee., (8888) 88, 888. |
[186] | Meeeee, M.; Meeeee, M., Meeee. Meee., (8888) 88, 888; Meeee. Meee. Mee. Me. Meee., (8888) 88, 888. |
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