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Radical-based transformation of vicinal diols to olefins via thioxocarbamate derivatives: a simple approach to 2',3'-didehydro-2',3'-dideoxynucleosides

Makoto Oba, Mitsuteru Suyama, Atsushi Shimamura and Kozaburo Nishiyama*

*Department of Material Science and Technology, Tokai University, 317 Nishino, Numazu, Shizuoka 410-0395, Japan, Email: nishiyamwing.ncc-u-tokai.ac.jp

M. Oba, M. Suyama, A. Shimamura, K. Nishiyama, Tetrahedron Lett., 2003, 44, 4027-4029.

DOI: 10.1016/S0040-4039(03)00847-5


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Abstract

Bis-O-thioxocarbamate derivatives of vicinal diols are reduced with tris(trimethylsilyl)silane in the presence of azobisisobutyronitrile to afford the corresponding olefins in good yields. 2',3'-didehydro-2',3'-dideoxy analogs of adenosine, guanosine, inosine, cytidine and uridine were prepared.

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Details

The document describes a method for transforming vicinal diols into olefins using thioxocarbamate derivatives, specifically focusing on the synthesis of 2',3'-didehydro-2',3'-dideoxynucleosides. The process involves reacting vicinal diols with phenyl isothiocyanate to form bis-O-thioxocarbamate derivatives, which are then reduced using tris(trimethylsilyl)silane and azobisisobutyronitrile (AIBN) to yield olefins. This method was applied to ribonucleosides to produce 2',3'-didehydro-2',3'-dideoxynucleosides, which are known for their antiviral properties against HIV. The study demonstrated that the tris(trimethylsilyl)silane–AIBN system is effective for this transformation, providing good yields. The method offers a simpler and more efficient alternative to existing procedures, such as the bisxanthate method, for preparing these unsaturated nucleosides. The document also includes experimental details, reaction conditions, and yields for various reducing agents and initiators, highlighting the optimal conditions for achieving high yields. This approach is significant for the synthesis and modification of complex molecules, particularly in the development of antiviral agents.


Radical-based deoxygenation of aliphatic alcohols via thioxocarbamate derivatives

M. Oba, K. Nishiyama, Tetrahedron, 1994, 50, 10193-10200. DOI: 10.1016/S0040-4020(01)81751-8


Key Words

Barton-McCombie reaction, Tris(trimethylsilyl)silane


ID: J72-Y2003-780