Reduction of acetylenic tellurides

The reduction of acetylenic tellurides to the vinylic ones is achieved by treatment with NaBH4 in EtOH. The formal unusual reduction of the carbon triple bond by NaBH4 can be rationalized involving the attack of a hydride ion to the tellurium atom producing a tellurol and an acetylenic anion followed by the addition of the tellurolate anion to the acetylene, DIBAL-H has later been employed as a reducing agent.  

---

A more extensive and detailed study of these reactions (i. e. 32 to 33) was carried out by Dabdoub et al., who found that two equivalents of Cp2Zr(H)Cl are needed for complete consumption of acetylenic tellurides 35 (Scheme 4.24) [51]. Solubilization of Cp2Zr(H)Cl in the reaction medium (THF) is apparently not a sufficient indication of educt consumption when only 1.1 equivalents are employed (e. g., following a proton quench, 58% of the product 37 and 41% of the acetylenic telluride 35 were recovered). Furthermore, care must be taken to avoid Cp2ZrH2, potentially present following the Buchwald route [3] to Cp2Zr(H)Cl, since Csp—Te bond reduction can occur to a significant extent in the presence of this dihydride or of residual LAH. 

Alkyl- and aryltellurols generated in situ by the well-established reduction of ditellurides with NaBH /EtOH add to terminal acetylenes, giving (Z)-vinylic tellurides. "" ... 

When the polarographic reduction of phenyl(4-methylphenyltelluro)acetylene was examined in MeCN in the presence of benzoic acid, the first reduction wave corresponding to the 2-electron electrochemical cleavage of the Csp—Te bond was progressively superseded by the 4-electron process of the hydrogenation of the triple bond. This reduction has been interpreted as involving an electron transfer to the adsorbed substrate yielding an anion radical, which after protonation and further reduction would form the saturated telluride (Scheme 1). 

---