2.4.1.3 Reductive Dehydroxylation via Thiocarbonyl and Selenides Derivatives
Reductive dehydroxylation via thiocarbonyl and selenide derivatives in presence of TBTH is an important method in synthetic organic chemistry. The thioacylation or selenation of alcohols gives thioesters or selenides which is then treated with Bu3SnH-AIBN reagent to give the desired dehydroxylated product (Scheme 4). The advantage of this method is that it works in such cases where other methods fail.
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Scheme 4 |
Mechanism
The tributyltin radical reacts with the sulfur atom to give a radical intermediate which then cleaves to give the desired radical and reacts with TBTH to regenerate the tributyltin radical and the product (Scheme 5).
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Scheme 5 |
Examples:
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D. P. Curran, D. M. Rakiewicz, Tetrahedron 1985, 41, 3943. |
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P. Dowd, S. C. Choi, J. Am. Chem. Soc. 1987, 109, 6548. |