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Kobayashi, S., Science of Synthesis: Water in Organic Synthesis, (2012) 1, 855.
Palladium-catalyzed allylic amination is a well-established method for the synthesis of allylamines. Indeed, since the 1980s, a variety of nitrogen nucleophiles have been developed for this useful transformation.[1–7] However, although ammonia is one of the most attractive nitrogen sources from a cost and atom-economical point of view,[8–23] there are no reports on the use of ammonia for metal-catalyzed allylic amination providing primary amines (one example of iridium-catalyzed allylic amination of methyl cinnamyl carbonate using a dioxane solution of ammonia to give the corresponding secondary amine exclusively has been reported[17]). Far from that, some authoritative review articles on allylic aminations mention that “ammonia does not react”[2] or “ammonia fails to act as an effective nucleophile for π-allylpalladium”.[1] Due to “the failure of ammonia,”[24] a variety of ammonia surrogates such as 4-toluenesulfonamide,[25] phthalimide,[26] iminodicarboxylic acid di-tert-butyl ester,[27] and sodium azide[28] have been used in allylic amination to synthesize primary amines.[2,29,30] In general, difficulty in the use of ammonia for metal-catalyzed processes arises because (i) many kinds of transition metals are deactivated by ammonia to give stable amine complexes, and (ii) if a reaction forms a primary amine, this product is more reactive than ammonia and causes problematic over-reactions.
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88 | 8,8-eeeeeee | 8:8 | 8.88 | 88 | 88 | – | 8 | 8 |
88e | 8,8-eeeeeee | 8:8 | 8.88 | 88 | 88 | 88:8 | 88 | 88 |
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References
[1] | Meeeeeee, M. M., Me Meeeeeeeeeeee Meeeeee Meeeeeeee, Meeee, M. M.; Meeeeee, M., Mee.; Meeeeeee: Meeeee, (8888); Mee. 8, e 888. |
[2] | Meeeeeeee, M.; Møeeeeeee, M. M., Meee. Mee., (8888) 88, 8888. |
[3] | Meeee, M. M.; Mee Meeeee, M. M., Meee. Mee., (8888) 88, 888. |
[4] | Meeee, M. M., Meee. Meeee. Meee., (8888) 88, 8. |
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[9] | Meeeee, M. M. M.; Meeee, M., Meee. Mee., (8888) 888, 8; eee eeeeeeeeee eeeee eeeeeee. |
[10] | Meeeeee, M.; Meeeee, M.; Meeeeeeee, M., M. Me. Meee. Mee., (8888) 888, 8888. |
[11] | Meee, M.; Meeee, M.; Meeeee, M. M.; Meeeeee, M. M., Meeeeeeeeee Meee., (8888) 88, 8888. |
[12] | Meeee, M.; Meeeee, M. M.; Meeee, M.; Meeeee, M., Mee. Meee., (8888) 8, 8888. |
[13] | Meeeeeee, M.; Meeeeeeeeeeee, M.; Meeeeeeeee, M. M., Meeeeeeeeee, (8888) 88, 8888. |
[14] | Meeeeeee, M.; Meeeeeee, M.; Meeeeee, M. M., Meee. Meeeee. (Meeeeeeee), (8888), 8888. |
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[18] | Meeeeeee, M.; Meeee, M.; eee Meee, M.; Meee, M. M.; Meeeee, M.; Me Mee, M. M., Meeee. Meee. Mee. Me., (8888) 88, 8888. |
[19] | Meeeeeeeee, M.; Meeeeeee, M., Meeee. Meee. Mee. Me., (8888) 88, 8888. |
[20] | Mee, M.; Meeee, M., Meee. Meeeee. (Meeeeeeee), (8888), 8888. |
[21] | Mee, M.; Meeeeeeee, M., Meeee. Meee. Mee. Me., (8888) 88, 888. |
[22] | Meeeeeeee, M.; Meeeee, M.; Meeeeee, M., Meee. Meeeee. (Meeeeeeee), (8888), 888. |
[23] | Meeeeee, M.; Meeeee, M.; Meeeeeeee, M., Mee. Meeee., Meee. Mee. MM, (8888), 888. |
[24] | Meeee, M. M.; Meeeee, M., M. Mee. Meee., (8888) 88, 8888. |
[25] | Meeeeöe, M. M.; Meeeeeee, M.; Mäeeeeee, M.-M., Meeeeeeeeee Meee., (8888) 88, 8888. |
[26] | Meeee, M.; Meeeeee, M.; Meeeeeee, M.; Meeeeeeee, M., Meee. Meee. Mee. Mee., (8888) 88, 8888. |
[27] | Meeeeee, M. M.; Meee, M.; Åeeeeeee, M.; Meeeeeee, M., M. Mee. Meee., (8888) 88, 8888. |
[28] | Meeeeeeee, M.-M.; Meeeeeeee, M.; Meeee, M.; Meeeeeee, M., M. Mee. Meee., (8888) 88, 8888. |
[29] | Meeeeeee, M.; Meeeeeee, M.; Meeeeeee, M., Meeee. Meee. Mee. Me., (8888) 88, 8888. |
[30] | Meeeeeee, M.; Meeeee, M. M.; Meeeee, M.; Meeeeeee, M. M., Meeee. Meee. Mee. Me., (8888) 88, 8888. |
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[32] | Meeeee, M.; Meeeeeeee, M., eeeeeeeeeee eeeeeee. |
[33] | Meeee, M.; Mee, M.; Meeeee, M.; Meeeee, M. M.; Meeee, M., M. Meee. Mee., Meeeee Meeee. 8, (8888), 8888. |
[34] | Meeeeeeee, M.; Meeeee, M.; Meeeeeeee, M.; Meeee, M.; Meeeeeeee, M., Meee. Meee., (8888), 888. |
[35] | Meeeee, M.; Meeee, M.; Meee, M.; Meeeeeee, M., Meeeeee, (8888), 888. |