Self and cross-metathesis of allylisothiocyanate with alkyl esters by grubbs 2nd generation catalyst

Bohari Mohd Yamin, NorWahida Awang, Sara Maira M Hizam, SitiAishah Hasbullah

Abstract


Allylisothiocyanateundergoes self-metathesis by 2nd generation Grubbs catalyst to give 1,4-disothiocyanatobut-ene together with the release of styrene and phosphine ligands. Despite the release of both ligands cross metathesis with methyl oleate, ethyl oleate and ethyl linoleatestill gave some targeted cross and self-metathesis products.1-isothiocyanatoundec-2-ene was detected in all the cross-metathesis reaction. Methyl11-isothiocyanatoundec-9-enoate and ethyl-11-isothiocyanatoundec-9-enoateare products of another cross-metathesis with methyl oleate and ethyl oleate respectively.  Under the reaction conditionno other cross product with ethyl linoleate was detectedexcept the formation of side products ofcarbene species possibly due to side reactions such as isomerization and addition. The formation of 1-isothiocyanatomethylstyreneis the result of the cross metathesis between allylisothiocyanate and styrene. The study indicated that the sulfur atom is more sensitive than oxygen atom to interact with the catalyst resulting in the release of the phosphine and styrene from catalytic cycle.  Therefore a suitable protecting agent is necessary to sustain the catalytic cycle.


Keywords


Allylisothiocyante, cross metathesis, methyl esters, ruthenium catalyst

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References


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