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α,α-Amino acids bearing a ring of less than 12 members, as well as those with other appendants such as Aib have been reported. 12-membered ring: a) M. Saviano, R. Iacovino, V. Menchise, E. Benedetti, G. M. Bonora, M. Gatos, L. Graci, F. Formaggio, M. Crisma, C. Toniolo, Biopolymers 2000, 53, 200-212;
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Direct dialkenylation of dimethylmalonate (4a) in the presence of an excess amount of a base (5 equiv Na in methanol) and allyl bromide (5 equiv) resulted in the formation of the monoallyl malonate (55 % yield), together with some diallyl malonate (12 % yield).
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1242337880
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note
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This phenomenon is also seen with acyclic long aliphatic substituents at the α position. In the case of n-propyl disubstitution (13a), the intermediate isocyanate (15a) can react with benzyl alcohol to give the N-Z derivative (14a). (Diagram Presented).
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39
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1242292793
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note
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40
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0029912748
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Structure minimizations were performed with a suite of programs: MacroModel version 8.1., Schrödinger, L. L. C. OPLS-AA force field: W. L. Jorgensen, D. S. Maxwell, J. Tirado-Rives, J. Am. Chem. Soc. 1996, 118, 11225-11235.
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1242292797
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note
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Increased hydrophobicity of the peptides caused greater nonspecific adsorption onto the glass and plastic surfaces of the equipment used for their purification, which lowered the yield.
-
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47
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1242270347
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note
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48
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