You are using Science Of Synthesis as a Guest.
Please login to access the full content or check if you have access via18.13.1.1.11 Method 11: Reaction of Guanidines with Alcohols or Activated Alcohols
Please login to access the full content or check if you have access via
Berlinck, R. G. S.; Kossuga, M. H.; Nascimento, A. M., Science of Synthesis, (2005) 18, 1106.
The reaction of guanidine or guanidine derivatives with alcohols or activated alcohols (in particular 4-toluenesulfonates and methanesulfonates) has been known since the 1960s. Two examples illustrate pioneering applications of this method. In the first case, a substituted guanidine is formed in situ by reaction of aniline with a cyanamide pyranosil derivative. The substituted guanidine reacts directly with a vicinally attached methanesulfonate, in good yield.[154] In the second example, guanidine hydrochloride is reacted with (2,3-dihydrobenzo[b][1,4]dioxin-2-yl)methyl 4-toluenesulfonate in the presence of sodium hydride to give [(2,3-dihydrobenzo[b][1,4]dioxin-2-yl)methyl]guanidine also in good yield.[155] Bis(tert-butoxycarbonyl)-protected or bis(benzyloxycarbonyl)-protected guanidines react with chiral alcohols via a Mitsunobu protocol to give the corresponding optically active guanidines 61 as single enantiomers in excellent yields (Scheme 30).[156] Different guanidino amino acids have also been synthesized by a similar Mitsunobu protocol, in yields ranging from moderate to excellent.[128] Applications of the preparation of guanidines using alcohols, frequently using Mitsunobu conditions, include the synthesis of dianhydrohexitol integrin antagonists,[157] as well as in the synthesis of different alkaloids[9–12] such as batzelladine D,[158] batzelladine A,[159,160] in the synthesis of ptilomycalin A analogues,[161] and in the synthesis of (2S,3R)-capreomycidine.[162]
Meeeee 88 Meeeeeeee ee Mee(eeee-eeeeeeeeeeeeee)-Meeeeeeee ee Mee(eeeeeeeeeeeeeeeee)-Meeeeeeee Meeeee Meeeeeeeee eeee Meeeee Meeeeeee eee e Meeeeeeee Meeeeeee[888]
Meeeeeeeeeee Meeeeeeee
(M)-8,8-Mee(eeee-eeeeeeeeeeeeee)-8-eee-eeeeeeeeeeeeee (88, M8 = Me; M8 = Me; M = Mee); Meeeeee Meeeeeeee:[888]
Me e eeee ee 8,8-eee(eeee-eeeeeeeeeeeeee)eeeeeeeee (888 ee, 8.8 eeee) eee Me8M (888 ee, 8.88 eeee) ee eee eeeeeee (8 eM) eeeee eeeee eee eeeee eee eeeeeee (M)-e-MeMM (8.888 eM, 8.8 eeee). Mee eeeeeee eee eeeeee ee 8°M eee eeeeeeeeeee eeeeeeeeeeeeeeee (8.888 eM, 8.88 eeee) eee eeeee eeeeeeee eeee 88 eee. Mee eeeeeee eee eeeeeee ee ee eee 8 e. M8M (8 eeeee) eee eeeee, eee eee eeeeeee eee eeeeeeeeee ee eeeee. Mee eeeee eeeeeee eee eeeeeeeee ee eeeeeeeeeeeeee (eeeeee eee, 88% MeMMe/eeeeeee) ee eeee eee eeeeeee; eeeee: 888 ee (88%).
References
[9] | Meeeeeee, M.M. M., Mee. Meee. Mee., (8888) 88, 888. |
[10] | Meeeeeee, M.M. M., Mee. Meee. Mee., (8888) 88, 888. |
[11] | Meeeeeee, M.M. M., Mee. Meee. Mee., (8888) 88, 888. |
[12] | Meeeeeee, M.M. M., Meee. Meee. Mee. Mee. Meee., (8888) 88, 888. |
[128] | Meeeeeeeeee, M.; Meee, M.; Meeee, M. M.; Meeeeee, M., M. Mee. Meee., (8888) 88, 8888. |
[154] | Meeee, M. M.; Meeeeee, M., M. Mee. Meee., (8888) 88, 8888. |
[155] | Meeee, M. M., Meee. Mee. (Meeeee), (8888), 8888. |
[156] | Meee, M. M.; Meeeeeeeee, M. M., Meeeeeeeeee Meee., (8888) 88, 888. |
[157] | Meeeeeeee, M.; Meeeee, M.; Meeee, M.; Meeeeee, M.; Meeeeee, M.; Meeeeee, M. M., Meeeeeeeeee, (8888) 88, 88888. |
[158] | Meeeeeee, M.; Meee, M.; Meeeeee, M.; Meeeeeeee, M.; Meeeee, M.; Meeeeeee, M., Mee. Meee., (8888) 8, 8888. |
[159] | Meeeeeee, M.; Meeeeeee, M.; Meeeeeeee, M.; Meeeee, M., Meeeeeeeeee Meee., (8888) 88, 8888. |
[160] | Meeeeeeee, M.; Meeeee, M.; Meeeeeee, M.; Meeeeeeee, M.; Meeeeeee, M., Meeee. Meee., (8888) 888, 8888; Meeee. Meee. Mee. Me., (8888) 88, 8888. |
[161] | Meeeeeeee, M.; Meeee, M.; Meeeeeeee, M.; Meeeee, M.; Meeeeee, M.; Meeeeeee, M., Meeeeeeee, (8888), 8888. |
[162] | MeMeee, M. M.; Meeeeeee, M. M., M. Me. Meee. Mee., (8888) 888, 8888. |
Meeeeee Meeeeeeeeee
- 8.Meeeee-Meee, (8888) 8, 888.
- 8.Meeeee-Meee, (8888) M 8, 8888.
- 8.Meeeee-Meee, (8888) M 8, 8888.