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Stereoselective aminoacylation of a dinucleoside monophosphate by the imidazolides ofDl-alanine and N-(tert-butoxycarbonyl)-Dl-alanine

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Summary

The aminoacylation of diinosine monophosphate (IpI) was studied. When the acylating agent was the imidazolide of N-(tert-butoxycarbonyl)-Dl-alanine, a 40% enantiomeric excess of thel isomer was incorporated at the internal 2′ site and the positions of equilibrium for the 2′⇆3′ migration reaction differed for theD andl enantiomers. The reactivity of the nucleoside hydroxyl groups decreased in the order 2′(3′)>internal 2′>5′, and the extent of reaction was affected by the concentration of the imidazole buffer (pH 7.1). In contrast, reaction of IpI with the imidazolide of unprotectedDl-alanine led to an excess of theD isomer at the internal 2′ site, while reaction with the N-carboxy anhydride ofDl-alanine proceeded without detectable stereoselection. The relevance of these results to the evolution of optical activity and the origin of genetically directed protein synthesis is discussed.

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Abbreviations

ImpA:

adenosine 5′-phosphorimidazolide

poly(U):

polyuridylic acid

ApA:

adenylyl-(3′–5′)-adenosine

Boc:

N-(tert-butoxycarbonyl)

poly(A):

polyadenylic acid

poly(C):

polycytidylic acid

poly(G):

polyguanylic acid

Ala-Im:

N-(alanyl)imidazole

CpA:

cytidylyl-(3′–5′)-adenosine

UpC:

uridylyl-(3′–5′)-uridine

IpI:

inosinylyl-(3′–5′)-inosine

Boc-Ala-Im:

N-[N-(ter-butoxycarbonyl)alanyl]imidazole

Boc-Ala:

N-(tert-butox-ycarbonyl) alanine

DMF:

N,N-dimethylformamide

Cbz-Ala:

N-(benzyloxycarbonyl)alanine

UV:

ultraviolet

NMR:

nuclear magnetic resonance

HPLC:

high-performance liquid chromatography

Tris:

tris(hydroxymethyl)aminomethane

EDTA:

ethylenediaminetetraacetic acid

Ino:

inosine

Ip:

inosine 3′-phosphate

I>p:

inosine 2′,3′-cyclic phosphate

5′-Boc-Ala-2′,3′-O-isopropylidene-Ino:

5′-O-[N-(ter-butoxycarbonyl)alanyl]-2′,3′-O-isopropylideneinosine

5′-Ala-Ino:

5′O(alanyl)inosine

2′-Boc-Ala-Ino:

2′-O-[N-(tert-butoxycarbonyl)alanyl]inosine

3′-Boc-Ala-Ino:

3′-O-[N-(tert-butoxycarbonyl)alanyl]inosine

5′-Boc-Ala-IpI:

5′-O-[N-(tert-butoxycarbonyl)alanyl]inosinylyl-(3′–5′)-inosine

internal-2′-Boc-Ala-IpI:

2′-O-[N-(tert-butoxycarbonyl)alanyl]inosinylyl-(3′–5′)-inosine

2′-Boc-Ala-IpI:

inosinylyl-(3′–5′)-3′-O[N-(tert-butoxycarbonyl)alanyl]inosine

5′-Ala-IpI:

5′-O-(alanyl)inosinylyl-(3′–5′)-inosine

internal-2′-Ala-IpI:

2′-O-(alanyl)inosinylyl-(3′–5′)-inosine

2′(3′)-Ala-IpI:

inosinylyl-(3′–5′)-2′(3′)-O-(alanyl)inosine

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  1. Department of Chemistry, Cornell University, 14853, Ithaca, New York, USA

    Albert T. Profy & D. A. Usher

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  1. Albert T. Profy
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  2. D. A. Usher
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Profy, A.T., Usher, D.A. Stereoselective aminoacylation of a dinucleoside monophosphate by the imidazolides ofDl-alanine and N-(tert-butoxycarbonyl)-Dl-alanine. J Mol Evol 20, 147–156 (1984). https://doi.org/10.1007/BF02257375

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  • DOI: https://doi.org/10.1007/BF02257375

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